Report EP 93 - 1315 November 1993 Confidential

DEOlLlNG MANUAL
Revision 1.1

Author:

A. C. Lawrence, EPDi421

Reviewed by: K. M. Perrin, EPDi421 Approved by: G. 0. Hajek, EPD/42

This dociinient I S confidential Neither the whole nor any part of this document m a y he ilisclosed to any third party without the !mor written consent of Shell Internationale Petroleum Maatschappij B.V., The Hague. the Netherlands. The copyright of this docuiiieiit is vested in Shell lriteriiationale Petroleum blaatschappi] B V.. The Hague. the Netherlands All rlyhts reserved. Neither the whole nor any pan of this docuinent m a y he reproduced, stored in airy retrieval systciii ot traiisniitled In aiiy form or hy any means (electronic, mechanical. reprographic. recording or otherwise) withoot the prior writlnri consent of the copyright owner

SHELL INTERNATIONALE PETROLEUM MAATSCHAPPIJ B.V., THE HAGUE
Exploration and Production

Revision history

REVISION HISTORY

Revision
Draft

Issue date

_____

By

Revision details
First draft of revised manual. Developed from existing SIPM DehydratiodDeoiling Manual EP 89-1 50. Update based on literature searches of SlPM EP report database, in-house files, OWTC test work and a questionnaire circulated to operating companies. Diagrams not included. Updated based on comments received on the Draft. Significant changes included the inclusion of all diagrams, a section introducing sludge treatment, clarification of iso-kinetic and isoenergetic sampling, inclusion of tables summarising the performance of equipment in tests, trials and operating installations and an appendix summarising the equations used to predict hydrocyclone performance. Updated with remaining comments received from Revision 1.O issue. Equations in Appendix A and B corrected. Sizing of sampling quill added to Appendix B. Section 7 updated. Results from Galai trial included.

14 May 1993 Allan Lawrence EPD/42I

Revision 1 .O

16 Aug 1993 Allan Lawrence EPD/42 1

Revision 1.1

S Nov 1993

Allan Lawrence EPD/42 1

Corrections

CORRECTIONS - ADDITIONS - SUGGESTIONS
This Deoiling Manual will only remain accurate and relevant if feedback is received from operating companies and all other users. Users are invited to forward any relevant information such as corrections to information given i n this manual, additional information on equipment installations, performance trials or new developments and any suggestions for improvements to this manual such as changes in structure or emphasis, new sections or topics for inclusion etc. This page can be photocopied and completed, including attachments as required, and forwarded to the address given below.

From: Company: Location:

Date: Indicator: TeVFax:

Forward to: SIPM, Posthus 162, 2501 AN Dcn Haag, The Netherlands - Attention EPD/42

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SIPM Deoiliiig M ~ i i i i i dEP , 93-1335. Rev 1.1, Nov 1993, File iiamr = 0TITLE.DOC

Table of contents

1

.

INTRODUCTION
1.1. 1.2. 1.3. 1.4. 1.5. 1.6. 1.7. 1.8.

................................................................................................................

1-1
1-1 1-1 1-1 1-1 1-2 1-3 1-3 1-3

GENERAL ........................................................................................................................... PURPOSE OF MANUAL .....................................................................................................

................................................................................................................... ORDER OF DOCUMENT PRECEDENCE............................................................................ STRUCTURE OF DEOlLlNG MANUAL............................................................................... INFORMATION BASE......................................................................................................... EQUIPMENT BRANDS AND SUPPLIERS........................................................................... ABBREVIATIONS ...............................................................................................................
DISTRIBUTION

2

.

CHARACTERISATION OF WASTE WATER
2.1. 2.2. GENERAL
2.2.1. 2.2.2. 2.2.3. 2.2.4. 2.2.5.

.....................................................................

2-1
2-1
2-1 2-1 2-2 2-2 2-3 2-3 2-5 2-5 2-6 2-6 2-7 2-7 2-7 2-7 2-8

...........................................................................................................................

SOURCES OF WASTE WATER ..........................................................................................

Produced water ...................................................................................................... Ballast water .......................................................................................................... Process water ........................................................................................................ Drainage water ...................................................................................................... Other waters ..........................................................................................................

2-1

2.3.

CONTAMINANTS OF WASTE WATER ...............................................................................
2.3.1 . 2.3.2. 2.3.3. 2.3.4. 2.3.5. 2.3.6. 2.3.7. 2.3.8. 2.3.9. 2.3.10.

Hydrocarbons derived from production streams ..................................................... Treatment chemicals.............................................................................................. Suspended solids ................................................................................................... Heavy metals ......................................................................................................... Salinity .................................................................................................................. pH ......................................................................................................................... Hardness ............................................................................................................... Thermal contamination .......................................................................................... Dissolved oxygen ................................................................................................... Organic carbon ......................................................................................................

2-3

2.4.

DROPLET SIZE DISTRIBUTIONS

.......................................................................................

2-8

3

.

EMULSIONS
3.1.

......................................................................................................................
General................................................................................... Distribution of phases ............................................................... Stability ............................................................................................. Size distributions................................................................

3-1
3-1 3-1

DEFINITIONS......................................................................................................................
3.1 .1. 3.1 .2. 3.1 .3. 3.1.4.

........................ ......................

3-1

3.2.

FORMATION OF EMULSIONS ...........................................................................................
3.2.1. 3.2.2. 3.3.1, 3.3.2. Formation locations ............................................................................................... Mixing energy and droplet size distributions............................................................

3-2 3-2

3-2

3.3.

STABlLlSATlON OF EMULSIONS......................................................................................

Immiscible liquids .................................................................................................. Surface tension ......................................................................................................

3-2
3-2 3-2

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3.3.3. 3.3.4. 3.3.5. Interfacial tension ................................................................................................... Contact angles and wetting of solids....................................................................... Emulsion stabilisers ............................................................................................... General .................................................................................................................. Emulsion breaking chemicals ................................................................................. Other methods of emulsion treatment ..................................................................... 3-3 3-3 3-4

3.4.

TREATMENT OF EMULSIONS ...........................................................................................
3.4.1. 3.4.2. 3.4.3.

3-6

3-6 3-6 3-8

4 . WATER DISPOSAL
4.1. 4.2.

..........................................................................................................
.........................................................................................................

4-1

GENERAL ........................................................................................................................... 4-1 SURFACE DISPOSAL
4.2.1. 4.2.2. Regulatory discharge limitations ............................................................................. Setting of environmental discharge standards......................................................... 4-1 4-3 4-3 4-3 4-4 4-5

4-1

4.3.

WATER INJECTION ............................................................................................................
4.3.1. 4.3.2. 4.3.3. 4.3.4.

General .................................................................................................................. Water compatibility ................................................................................................ Permeability impairment......................................................................................... Secondary waste water streams .............................................................................

4-3

4.4.

DISPOSAL INJECTION ....................................................................................................... 4-5
4.4.1. 4.4.2. General .................................................................................................................. 4 . 5 Water quality constraints ........................................................................................ 4-5 General .................................................................................................................. Disposal options ..................................................................................................... Sludges .................................................................................................................. 4-6 4-6 4.7

4.5.

SECONDARY (REJECT) STREAM DISPOSAL ...................................................................
4.5.1 . 4.5.2. 4.5.3.

4-6

5 . WASTE WATER SAMPLING ............................................................................................
5.1. 5.2.

5-1

GENERAL ........................................................................................................................... 5-1 SAMPLE POINTS 5.2.1. Location of sampling points ....................................................................................
5.2.2. 5.2.3.

................................................................................................................

Orientation of sampling points ................................................................................ 5-2 Design of sampling quills........................................................................................ 5-2 Materials ................................................................................................................ 5-3 Cleaning of sample containers................................................................................ 5-4

5-1

5-1

5.3.

SAMPLE CONTAINERS......................................................................................................
5.3.1. 5.3.2.

5-3

5.4. 5.5.

SELECTION OF SAMPLING METHOD ............................................................................... ROUTINE SAMPLING .........................................................................................................
5.5.1. 5.5.2. 5.5.3.

5-4 5-5

Introduction............................................................................................................ 5-5 lsokinetic conditions ............................................................................................... 5-5 Procedure for routine sampling............................................................................... 5-6

5.6.

SAMPLING TO MEASURE DROPLET SIZE DISTRIBUTIONS
5.6.1. 5.6.2. 5.6.3.

Introduction............................................................................................................ 5-6 Sampling procedure to determine droplet size distribution....................................... 5-7 Effect of process pressure on sampling and droplet size distributions ..................... 5-7

............................................

5-6

5.7.

SAMPLE PRESERVATION AND STORAGE
5.7.1. 5.7.2. 5.7.3.

Introduction............................................................................................................ 5-8 Chemical Preservation ........................................................................................... 5-9 Sample storage ...................................................................................................... 5-9

.......................................................................

5-8

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Table o f contents
6

.

WASTE WATER ANALYSIS
6.1. 6.2. GENERAL
6.2.1 . 6.2.2. 6.2.3. 6.2.4. 6.2.5.

........................................................................................................................... HYDROCARBONS.INFRARED ABSORPTION ANALYSIS ...............................................

.............................................................................................
~1

6-1

Introduction............................................................................................................ Sample preparation................................................................................................ Hydrocarbon extraction .......................................................................................... Removal of polar.compounds................................................................................. Infrared analysis .................................................................................................... Dispersed and dissolved hydrocarbons .................................................................. Gravimetric analysis .............................................................................................. Visible spectrum colourimetry ................................................................................ Gas chromatography ............................................................................................. Others ................................................................................................................... General..................................................................................................................

6-1 6-2 6-2 6-3 6-3 6-5 6-5 6-6 6-6 6-6

6-1

6.3.

HYDROCARBONS.OTHER METHODS
6.3.1 . 6.3.2. 6.3.3. 6.3.4. 6.3.5.

.............................................................................

6-5

6.4. 6.5.

ON-LINE OIL-IN-WATER ANALYSERS
6.4.1 . 6.5.1 . 6.5.2. 6.5.3. 6.5.4. 6.5.5.

..............................................................................

6-7
6-7

MEASUREMENTOF PARTICLE AND DROPLET SIZES

General.................................................................................................................. 6-8 6-8 Sampling ............................................................................................................... Potential problems in measuring droplet size distributions...................................... 6-8 Droplet size distribution analysers .......................................................................... 6-8 Particle size analyser trials ................................................................................... 6-10

....................................................

6-8

7. EQUIPMENT SELECTION AND SYSTEM INTEGRATION
7.1. 7.2. INTRODUCTION

...............................................

7-1
7-1
7-1 7-1 7-2 7-2 7-3 7-3 7-3 7-4 7-5 7-5 7-7 7-7 7-7 7-8 7-8 7-8 7-8 7-8

7.2.1. 7.2.2. 7.2.3. 7.2.4. 7.2.5. 7.2.6. 7.2.7. 7.2.8. 7.2.9. 7.2.10.

................................................................................................................. EQUIPMENT SELECTION AND SYSTEM DESIGN.............................................................

Introduction...................................................................................................................... Sources and magnitude of water streams (1) .................................................................... Identify contaminants in the waste water stream (2) .......................................................... Identify treated water quality requirements (3) ................................................................... Select a suitable process location for the water treatment system (4) ................................ Identify upstream methods of improving ease of water treatment (5)................................. Select the number of treatment stages (6) ........................................................................ Select the suitable deoiling equipment (7) ......................................................................... Treatment or disposal of secondary streams (8) ............................................................... System optimisation and integration (9) ............................................................................

7-1

7.3.1. 7.3.2. 7.3.3. 7.3.4. 7.3.5. 7.3.6. 7.3.7. 7.3.8.

7.3.

SYSTEM OPTlMlSATlON AND INTEGRATION CONSIDERATIONS

Introduction...................................................................................................................... Maximising droplet size .................................................................................................... Minimising the hydrocarbon content in the feed stream ..................................................... Production separators ...................................................................................................... Stable feed streams .......................................................................................................... Recycle streams ............................................................................................................... Mixing of water streams .................................................................................................... Treatment chemicals ........................................................................................................

..................................

7-7

7.4.

7 . 5 .
7.6.

............................................................. WATER CHARACTERISATIONCONSULTANCY SERVICES ............................................. PILOT PLANT TRIALS........................................................................................................
EXAMPLES OF WATER TREATMENT SCHEMES

7-9 7-9 7-9

8. DISPERSED HYDROCARBONS
8.1.
8.1 .1. 8.1.2.

....................................................................................

8-1-1

INTRODUCTION ..............................................................................................................

8-1-1 Scope of chapter ................................................................................................. 8-1-1 Equipment for dispersed hydrocarbons .Summary tables ................................... 8-1-1

Table of contents
8.2. 8.3. DEFINITIONS..................................................................................................................
8.2.1. Deoiling efficiencies............................................................................................

..

8-2-1

8-2-1

COALESCERS
8.3.1. 8.3.2. 8.3.3. 8.3.4. 8.3.5. 8.4.1. 8.4.2. 8.4.3.

General .............................................................................................................. Definitions .......................................................................................................... Performance variables........................................................................................ Installation/Configuration.................................................................................... Coalescer designs .............................................................................................. General .............................................................................................................. Floc separation .................................................................................................. Operation considerations.................................................................................... Introduction ........................................................................................................ performance variables........................................................................................ Installation/Configuration.................................................................................... Design guidelines ............................................................................................... Control configuration ..........................................................................................

................................................................................................................

8-3-1

8-3-1 8-3-1 8-3-1 8-3-2 8-3-2

8.4.

FLOCCULATION.............................................................................................................

8-4-1

8-4-1 8-4-1 8-4-2

8.5.

SKIMMING TANKS AND VESSELS ................................................................................
8.5.1. 8.5.2. 8.5.3. 8.5.4. 8.5.5. 8.6.1. 8.6.2. 8.6.3. 8.6.4.

8-5-1

8-5-1 8-5-1 8-5-1 8-5-1 8-5-2

8.6.

DISCHARGE CAISSONS.................................................................................................

Introduction ........................................................................................................ Design guidelines ............................................................................................... Caisson internals................................................................................................ Operational considerations................................................................................. Introduction........................................................................................................ Performance variables........................................................................................ Installation/Configuration.................................................................................... Design guidelines ...............................................................................................

8-6-1 8-6-1 8-6-1 8-6-2

8-6-1

8.7.

API SEPARATOR
8.7.1. 8.7.2. 8.7.3. 8.7.4.

............................................................................................................

8-7-1

8-7-1 8-7-1 8-7-2 8-7-2

8.8.

PLATE INTERCEPTORS .................................................................................................
8.8.1. 8.8.2. 8.8.3. 8.8.4. 8.8.5. Introduction........................................................................................................ Performance variables........................................................................................ Installation/Configuration.................................................................................... Design guidelines ............................................................................................... Operational considerations.................................................................................

8-8-1 8-8-1 8-8-3 8-8-4 8-8-5 8-9-1 8-9-1 8-9-1 8-9-8 8-9-9 8-9-11 8-10-1 8-10-1 8-10-1 8-10-5 8-10-6 8-10-7 8-10-7

8-8-1

8.9.

STATIC HYDROCYCLONE..............................................................................................
8.9.1. 8.9.2. 8.9.3. 8.9.4. 8.9.5. 8.9.6.

Introduction........................................................................................................ Definitions.......................................................................................................... Performance variables........................................................................................ InstallationlConfiguration.................................................................................... Control configuration.......................................................................................... Operational considerations ................................................................................

8-9-1

8.10. ROTARY HYDROCYCLONE .......................................................................................... 8-10-1
8.10.1 . 8.10.2. 8.10.3. 8.10.4. 8.10.5. 8.10.6. 8.10.7. Introduction ....................................................................................................... Definitions......................................................................................................... Performance variables....................................................................................... Installation/Configuration................................................................................... Design guidelines .............................................................................................. Control configuration......................................................................................... Operational considerations ................................................................................

8.11. CENTRIFUGES .............................................................................................................. 8-11-1
8.11.1. 8.1 1.2. 8.1 1.3. 8.1 1.4. 8.1 1.5. Introduction....................................................................................................... Performance variables....................................................................................... Installation/Configuration................................................................................... Control configuration......................................................................................... Operational considerations ................................................................................

8-11-1 8-11-1 8-11-2 8-11-4 8-1 1-4

8.12. INDUCED GAS FLOTATION..........................................................................................

8.12.1 . Introduction....................................................................................................... 8-12-1
SlPM Droiling Mimlvtl. EP 93.1315. Rev I.!,Nov 1993 Filr name = 0TlTLE.DOC

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Table of contents
8.12.2. 8.1 2.3. 8.1 2.4. 8.12.5. 8.12.6. 8.13.1. 8.13.2. 8.13.3. 8.13.4. 8.13.5. Performance variables ...................................................... :............................... Installation/Configuration.................................................................................. Design guidelines .............................................................................................. Control configurations ....................................................................................... Operational considerations................................................................................ Introduction....................................................................................................... Performance variables ...................................................................................... Installation/Configuration .................................................................................. Design guidelines .............................................................................................. Operational considerations................................................................................ Introduction....................................................................................................... Performance variables ...................................................................................... Installation/Configuration .................................................................................. Design guidelines .............................................................................................. Control configuration......................................................................................... Operational considerations................................................................................ Crushed nut shell deep bed media filters ........................................................... Introduction....................................................................................................... Performance variables ...................................................................................... Installation/Configuration.................................................................................. Design guidelines.............................................................................................. 8-12-3 8-12-6 8-12-7 8-12-7 8-12-8 8-13-1 8-13-2 8-13-4 8-13-5 8-13-5 8-14-1 8-14-2 8-14-5 8-14-6 8-14-6 8-14-6 8-14-7 8-15-1 8-15-1 8-15-1 8-15-2 8-16-1 8-16-1 8-16-2 8-16-2 8-16-2 8-17-1 8-17-2 8-17-3 8-17-3

8.13. DISSOLVED GAS FLOTATION

......................................................................................

8-13-1

8.14. DEEP BED MEDIA FILTRATION
8.14.1. 8.14.2. 8.14.3. 8.14.4. 8.14.5. 8.14.6. 8.14.7. 8.15.1. 8.15.2. 8.15.3. 8.1 5.4.

....................................................................................

&-14-1

8.15. CARTRIDGE FILTERS...................................................................................................

8-15-1

8.16. PRE-COAT FILTRATION ...............................................................................................
8.16.1 . 8.16.2. 8.16.3. 8.1 6.4. 8.16.5.

Introduction....................................................................................................... Performance variables ...................................................................................... Installation/Configuration .................................................................................. Design guidelines.............................................................................................. Operational considerations................................................................................ Introduction....................................................................................................... Performance variables ...................................................................................... Installation/Configuration .................................................................................. Membrane trials ................................................................................................

8-16-1

8.17. MEMBRANES
8.1 7.1 . 8.1 7.2. 8.1 7.3. 8.1 7.4.

................................................................................................................

8-17-1

9. DISSOLVED HYDROCARBONS
9.1. 9.2. 9.3. INTRODUCTION

....................................................................................

9-1-1
9-1-1 9-2-1
9-3-1 9-3-2 9-3-3 9-3-4 9-4-1 9-4-1 9-4-2 9-4-2 9-5-1 9-5-1 9-5-3 9-5-4 9-5-4

..............................................................................................................

LEVELS OF DISSOLVED HYDROCARBONS IN WATER ................................................ GAS STRIPPING..............................................................................................................
9.3.1. 9.3.2. 9.3.3. 9.3.4. Introduction......................................................................................................... Performance variables ........................................................................................ Installation/Configuration .................................................................................... Design guidelines................................................................................................

9-3-1

9.4.

STEAM STRIPPING .........................................................................................................
9.4.1 . 9.4.2. 9.4.3. 9.4.4.

Introduction......................................................................................................... Performance variables ........................................................................................ Installation/Configuration .................................................................................... Design guidelines................................................................................................

9-4-1

9.5.

BIOLOGICAL TREATMENT.............................................................................................
9.5.1. 9.5.2. 9.5.3. 9.5.4. 9.5.5.

Introduction......................................................................................................... Aerobic processes............................................................................................... Anaerobic processes........................................................................................... Performance variables ........................................................................................ Installation/Configuration ....................................................................................

9-5-1

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Table o f contents
9.6.
ACTIVATED CARBON 9.6.1. Introduction........................................................................................................ 9.6.2. Performance variables........................................................................................ .................................................................................... 9.6.3. Installation/Configuration SOLVENT EXTRACTION 9.7.1. Introduction ........................................................................................................ 9.7.2. Co-current extraction..........................................................................................
~~~

....................................................................................................

9-6-1 9-6-1 9-6-1 9-6-2 9-7-1 9-7-1 9-7-1

9.7.

.................................................................................................

10 NEW TECHNOLOGY

.

~~

......................................................................................................

10-1

10.1. GENERAL .......................................................................................................................... 0-1

10.2. OZONEILILTRAVIOLET 10.3. 10.4.

..................................................................................................... ADSORPTION ON MODIFIED ZEOLITES ......................................................................... MEMBRANE LIKE MATERIAL ..........................................................................................

10-1
10-1

10-1
0-1

10.5. PERVAPORATION.............................................................................................................

10.6. MEMBRANES FOR DISSOLVED HYDROCARBONS

........................................................

10-2

Appendix A
A.l.

.Emulsification and coalescence .................................................................... Introduction.......................................................................................................................
A.l .1 A.1.2 A.1.3
Mixing intensity ..................................................................................................... Prediction of droplet size ....................................................................................... Mixing energy in piping .......................................................................................... Optimum Mixing Intensity For Coalescence

A-I
A-1

A-1 A-1 A-2

A.2.

....................................................................

A-3

Appendix B Sampling t o determine droplet size
B.l. 8.2. 8.3. 8.4. 8.5. Introduction

.

...............................................................

8-1
B-1 B-1 8-2 8-5 B-6

....................................................................................................................... Calculation of the mixing intensity in the process line ................................................... Pressure drop in the sampling system ............................................................................ Sizing the sample quill for isokinetic conditions ............................................................ Contrast with iso-kinetic sampling ..................................................................................

Appendix C Published infrared analysis procedures
C.l List of IR analysis procedures C.2

.

.......................................................

C-1
C-1 C-2

............................................................................................. Key characteristics of identified IR analysis procedures ...................................................
monitor trials

Appendix

D.l Oil-In-Water Monitor Testing .Phase I D.l .1. General ................................................................................................................. D.1.2. Monitors tested...................................................................................................... D.1.3. Variables investigated ........................................................................................... D.1.4. Summary of results ...............................................................................................
I ’ u ~ : cv i i i

D .Oil-in-water

...............................................................................
................................................................................

D.1
D-1 D-1 D-1 D-2
D-1

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Table o f contents
D.2 Oil-In-Water Monitor Testing .Phase It D.2.1. General................................................................................................................. D.2.2. Monitors tested ..................................................................................................... D.2.3. Variables investigated ........................................................................................... D.2.4. Summary of results ............................................................................................... D.3 Oil-In-Water Monitor Testing .Phase 111

...............................................................................

D-2 D-2 D-2 D-3 D-3 D-4

..............................................................................

Appendix E .Particle size analyser trials
E.l.

............................................................................

E-1
E-1
E-1 E-1 E-1 E-1

OWTC particle size analyser trials E.l.l. General.................................................................................................................. E.1.2. Analysers tested .................................................................................................... E.1.3. Variables investigated ............................................................................................ E.1.4. Summary of results ................................................................................................ Galai CIS-1000 trials at KSLA E.2.1. Results of trial ........................................................................................................ E.2.2. Conclusions ...........................................................................................................

....................................................................................

E.2.

............................................................................................

E-2 E-2 E-2

Appendix F .Stokes law
F.l. F.2. Derivation

........................................................................................................

F-1
F-1 F-2 F-2 F-2 F-2 F-2 F-2

...........................................................................................................................

Variables In Stokes Law .................................................................................................... F.2.1 Droplet size ............................................................................................................ F.2.2 Gravitational acceleration....................................................................................... F.2.3 Viscosity ................................................................................................................ F.2.4 Density difference .................................................................................................. The Effect Of Temperature On Stokes Law

F.3.

......................................................................

Appendix G .Coalescer equipment and trials ....................................................................
G.l. G.2. Introduction G.2.1 G.2.2 G.2.3

G-1
G-1 G-1 G-1 G-1 G-2 G-2 G-2 G-2 G-2 G-2 G-3 G-3 G-3 G-3 G-3 G-3 G-3 G-3 G-3 G-3 G-3 G-3 G-4

...................................................................................................................... Knitmesh Dusec................................................................................................................
Knitmesh DC coalescing mesh

Description ........................................................................................................... Packaging............................................................................................................. Performance.........................................................................................................

G.3. G.4.

........................................................................................

Hydrocyclone coalescer G.4.1 Description ........................................................................................................... G.4.2 Packaging............................................................................................................. G.4.3 Performance......................................................................................................... MPE SP Pack G.5.1 Description ........................................................................................................... G.5.2 Packaging............................................................................................................. G.5.3 Performance......................................................................................................... Monosep Spiralsep Coalescer ......................................................................................... G.6.1 Description ........................................................................................................... G.6.2 Packaging............................................................................................................. G.6.3 Performance......................................................................................................... Sulzer Mellapak G.7.1 Description ........................................................................................................... (3.7.2 Packaging ............................................................................................................. G.7.3 Performance......................................................................................................... Upflow Filter/Coalescers

...................................................................................................

G.5.

.....................................................................................................................

G.6.

G.7.

.................................................................................................................

G.8.

..................................................................................................

Table of contents
G.9.

................................................................................... G.10. Skimovex lnverto Filter/Coalescer ................................................................................... G.11. Elf Anvar Filter/Coalescer ................................................................................................. G.12. Plate interceptors.............................................................................................................. G.13. Natco Performax ...............................................................................................................
Expandable fibrous bed coalescer

G-4 G-5 G-5 G-6 G-6

Appendix H .Plate pack sizing
H.l. H.2. H.3. H.4. H.5. H.6.
Introduction

.............................................................................................

H-1
H-1 H-1 H-2 H-2 H-3 H-4

....................................................................................................................... Reynolds number .............................................................................................................. Plate pack dimensions for droplet interception ..............................................................
............................................................................................................ Effect of Reynolds number ............................................................................................... Standard Shell CPI design ................................................................................................
Sizing a plate pack

Appendix I .Predicting hydrocyclone performance
1.1 Introduction 1.2 1.3

............................................................
1-1 1-1 1-1
1-1 1-2 1-2

1-1

........................................................................................................................... Cut size diameter ................................................................................................................... Cut size diameter correlations ..............................................................................................
1.3.1 1.3.2 1.3.3 Equilibrium orbit theory .......................................................................................... Residence time model ............................................................................................ Empirical model .....................................................................................................

1.4 Migration probability 1.5 1.6
1 . 7

............................................................................................................. Empirical migration probability correlations ....................................................................... Empirical pressure drop correlations ................................................................................... Application of correlations to hydrocyclone trials ...............................................................
1.7.1 1.7.2 North Cormorant trials ............................................................................................ OWTC trials ...........................................................................................................

1-2 1-3 1-3 1-3
1-3 1-3

1 . 8 Nomenclature

........................................................................................................................

1-4

Appendix J .Predicting levels of dissolved hydrocarbons
J.1, J.2. J.3. 5.4.
Introduction

................................................

J-1
J-1 J-1 J-2 5-3

........................................................................................................................ Theory ................................................................................................................................. Comparison with experimental and field results ..............................................................
Parameters affecting solubility

.........................................................................................

Appendix K .Dissolved hydrocarbons equipment comparison ........................................
K.l. K.2.

K-1
K-1
K-1

....................................................................................................................... Design basis ......................................................................................................................
Introduction

Table o f contents
K.3. Results

..............................................................................................................................

K-2

Appendix L Membrane trials
L.l. L.2. L.3. L.4. L.5. L.6. L.7. L.8. L.9. Introduction

-

...............................................................................................

1-1
1-1
1-1 1-2 1-2

....................................................................................................................... Alcoa Petrolox ................................................................................................................... SDI Extran .......................................................................................................................... X-Flow ................................................................................................................................ .. Stork-Wafilin ...................................................................................................................... Schelde-Delta ..................................................................................................................... WL Gore .............................................................................................................................
Hoogovens......................................................................................................................... Zenon .................................................................................................................................

1-2
1-2 1-2 1-2
1-3

Bibliography

.......................................................................................................

Bibliography-1
Bibliography-1 Bibliography-1 Bibliography-1

. 2. 3.
1

Introduction

........................................................................................................ Literature searches ............................................................................................ Index ...................................................................................................................

Table of contents

THIS PAGE HAS BEEN INTENTIONALLY LEFT BLANK

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1. Introduction

1.1.

GENERAL
The production of hydrocarbons is usually associated with the generation of a waste water stream which requires treatment to allow it to be disposed in a safe and environmentally acceptable manner. Over the four years since the last revision of this manual both the technical aspects of waste water treatment and the philosophies governing waste water treatment have undergone significant changes, especially in the light of increasing environmental awareness in the community and in industry. New information and developments that have been incorporated into this update of the Deoiling Manual include; The use of droplet size distribution as tool in optimising the design and operation of waste water treatment equipment. The results of independent equipment testing programs conducted at the Orkney Water Test Centre. Procedures for the sampling of oil-in-water dispersions. The use of more advanced deoiling equipment such as hydrocyclones and centrifuges. New waste water treatment technologies under development. The removal of dissolved hydrocarbons.

1.2.

PURPOSE OF MANUAL
This updated Deoiling Manual has been designed to satisfy the following major objectives. To provide background information on all aspects of water deoiling including water sampling, analysis and characterisation, hydrocarbon-in-water emulsions and the disposal of treated water. To provide users with an understanding of the design principles and performance characteristics of currently available equipment for the removal of dispersed and dissolved hydrocarbons. To provide guidelines for deoiling equipment selection and facilities design. To provide a listing of reports, documents, papers and equipment trials relevant to the selection, testing or operation of deoiling equipment.
It should be emphasised that this Deoiling Manual should not be considered to be a fixed set of rules or methods governing deoiling and associated topics. It should serve as an introduction and a foundation to these subjects, but not hinder further developments and advancements.

1.3.

DlSTRIB UTlON
Unless otherwise authorised by SIPM, the distribution of this document is confined to companies forming part of the Royal Dutch/Shell Group or managed by a Group company, and to contractors nominated by them.

1.4.

ORDER OF DOCUMENT PRECEDENCE
This Deoiling Manual forms the first stage of the updating of the SlPM Dehydration/Deoiling Manual (EP 89-0150, January 1989). All information relevant to deoiling from the current Dehydration/Deoiling Manual has been included or updated into this Deoiling Manual. Information more closely related to dehydration has not been included in this manual, but will be updated into a new Dehydration Manual in 1994. This update procedure will eventually result in the creation of the following two documents, which together will supersede the existing SlPM Dehydration/Deoiling Manual.

1. Introduction
Deoiling Manual (This document) Dehydration Manual Addressing the removal of hydrocarbons and other contaminants from water streams. Addressing the removal of water from hydrocarbon streams.

However, until the new Dehydration Manual is completed, this document (Deoiling Manual) will coexist with the current Dehydration/Deoiling manual. In general, the order of document precedence should be as follows; This document (Deoiling Manual) should be used for all information relevant to deoiling. The current Dehydration/Deoiling manual (EP 89-0150) should be used for information specific to dehydration. In the event of conflict, this document (Deoiling Manual) shall take precedence.

1.5.

STRUCTURE OF DEOlLlNG MANUAL
This Deoiling Manual has been divided into the following structure. Chapter 1 Chapter 2

-

Introduction - Forms the preamble to the Deoiling Manual, outlining the objectives, scope and organisation of the document. Characterisation of waste water Discusses the elements defining the character of waste waters such as the source of the waste water, typical contaminants, the distribution and nature of contaminants and measurements of water quality. Emulsions Discusses the characteristics, formation, stability and treatment of hydrocarbon in water emulsions. Water disposal Discusses the technical and environmental considerations governing the methods of water disposal, including both surface and subsurface disposal. Waste water sampling - Discusses the sampling procedures required to obtain representative samples of waste water, particularly for water containing dispersed hydrocarbon droplets. Waste water analysis Discusses the analysis methods required to determine the hydrocarbon content in waste waters, the measurement of dispersed and dissolved hydrocarbons, the performance of on-line oil-in-water analysers and the measurement of dispersed droplet size distributions. System design and integration Discusses the selection and application of deoiling equipment with emphasis on system integration. This approach recognises that the deoiling equipment forms only one part of the production process and must be integrated with other systems. Topics covered include the location of the deoiling equipment in the process train, the minimisation of emulsifying forces, the influence of direct and indirect addition of treatment chemicals on the deoiling process and the integration of recycling hydrocarbon reject streams into the process. Deoiling equipment Dispersed hydrocarbons Examines proven deoiling equipment in detail. Information provided includes design principles, process design requirements, deoiling performance, typical unit dimensions and weights and basic sizing guidelines. Where applicable, tables are given summarising the performance of the equipment in a range of Shell installations, pilot plant tests and field trials. Deoiling equipment Dissolved hydrocarbons Examines the range of processes available for the removal of dissolved hydrocarbons from water streams. New technology Briefly discusses a selection of new technologies currently under development for the treatment of waste waters.

-

Chapter 3 Chapter 4 Chapter 5

-

-

Chapter 6

-

-

Chapter 7

-

Chapter 8

-

-

-

Chapter 9

-

-

Chapter 10

-

Appendices

The Appendices cover a wide range of topics which cannot be easily incorporated into the text of the manual, particularly calculation methods such as mixing intensity calculations, plate pack sizing and methods for predicting the levels of dissolved hydrocarbons in

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I . Introduction

Bibliography The Bibliography lists all the references used for the compilation of this Deoiling Manual. If not available through local sources, these references can be requested from the SlPM Report Library EPD/52 or through SlPM EPD/4.

-

water.

1.6.

INFORMATION BASE
The starting point for this Deoiling Manual has been the 1989 SlPM Dehydration/Deoiling Manual (EP 89-0150). The deoiling sections of EP 89-0150 are now superseded by this updated Deoiling Manual. The additional information incorporated into this update of the Deoiling Manual has been taken from the following sources. i) ii) Literature survey of the SlPM STAIRS document database for reports related to deoiling and associated topics. Details of the keyword searches conducted are included in the Bibliography. Input from operating companies including; Requests for relevant references and documentation. Requests for comments on the existing Dehydration/Deoilingmanual. A questionnaire to identify the performance of existing deoiling equipment installations. iii) iv) Results of test work conducted at the Orkney Water Test Centre and experimental work conducted at KSLA. Discussions with equipment vendors.

1.7.

EQUIPMENT BRANDS AND SUPPLIERS
The commercial or proprietary nature of many items of deoiling equipment often requires the mention of specific equipment brand names or equipment suppliers. In some cases, a specific equipment brand may be used to illustrate the characteristics of a generic class of equipment. It should be clearly noted that the inclusion or exclusion of any process equipment, manufacturer or supplier from this manual should not be interpreted as representing a preference for a particular equipment design, manufacturer or supplier. To ensure a competitive market for deoiling equipment, alternatives to the equipment discussed in this manual should be actively sought wherever possible.

1.8.

ABBREVIATIONS
The following abbreviations have been used in the Deoiling Manual. AMS APHA API ASTM BOD BTEX C-H CCD COD CPI DC DAF DGF DOC E&P EPA GBS GOR HSE IGF IP IR Amsterdam Method Series (Analytical methods developed and documented by KSLA) American Public Health Association American Petroleum Institute American Society for Testing and Materials Biological Oxygen Demand Benzene, Toluene, Ethyl benzene, Xylene Carbon-Hydrogen Charge Coupled Device Chemical Oxygen Demand Corrugated Plate Interceptor Dissolved Carbon Dissolved Air Flotation Dissolved Gas Flotation Dissolved Organic Carbon Exploration and Production Environmental Protection Authority (USA) Gravity Based Storage Gas to Oil Ratio Health, Safety and Environmental Induced Gas Flotation Institute of Petroleum Infrared

SlPM Dcnilinx Moniiol. EP 93-1315. Rev 1.1, Nov 1993. File IKUW = IINTR0.DOC

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1. Introduction
ISF IS0 KSEPL
Induced Static Flotation International Organisation for Standardisation Royal Dutch/Shell Exploration and Production Laboratory Royal Dutch/Shell Laboratories Amsterdam Membrane Like Material Orkney Water Test Centre Parallel Plate Interceptor Shell lnternationale Petroleum Maatschappij B.V., The Hague Shell Method Series Total Carbon Total Dissolved Solids Total Organic Carbon Total Oxygen Demand Tilted Plate Interceptor Thornton Research Centre

KSLA

MLM OWTC PPI SIPM SMS TC TDS TOC TOD TPI TRC

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2. Characterisation o f waste water

2.1.

GENERAL
Each waste water stream is unique, with characteristics defined by a wide range of variables such as the water source, processing operations and directly or indirectly added chemicals. Correct characterisation of the waste water stream is essential to ensure the appropriate selection, design and operation of any deoiling system. This chapter discusses a number of the elements which define the characteristics of a waste water stream.

2.2.

SOURCES OF WASTE WATER
Waste water streams may originate from a number of sources, each giving the water stream particular characteristics. The selection of the correct treatment process for the waste water requires that the characteristics of all the waste water sources are taken into consideration.

2.2.1.

Produced water
The major source of waste water from production of oil.

E & P activities is produced water, particularly associated with the

The main component of produced water is normally the formation water that is initially present in the reservoir. Formation water should be regarded as being uniquely different from other waters, having existed for millions of years in contact with rock minerals and hydrocarbons, typically under conditions of high temperature and pressure. The produced water may also contain fluids associated with enhanced recovery schemes, particularly injection water. Breakthrough of injection water or other fluids associated with enhanced recovery schemes (e.g. polymers) to the producing wells will result in a change in the character of the produced water. The largest volumes of produced waters are associated with oil production, with gas production having significantly lower rates of produced water. Table 2.1 illustrates the magnitude of the waste water streams produced from a selection of oil and gas platforms in the North Sea. It can be seen that the waste water production from the oil platforms is several orders of magnitude greater than that of the gas platforms.
Table 2.1 Typical hydrocarbon discharges from a selection of North Sea oil and gas production platforms (1989) Oil platforms Gas platforms

Number of platforms measured Total oil or gas production Total produced water Total hydrocarbon discharge (11 Dispersed oil concentration Dissolved oil concentration Polar hydrocarbonconcentration smVd m3/d tonne/y mgn mgn msn

75,600 (475,500 bopd) 63,713
500

12

49,100,000 (1,734 MMscfd) 216 612

15

15.3 165.9 6.2

230.1

481.9

483.9

2.2.2.

Ballast water
Ballast water is a waste water stream generally associated with the storage of oil. The major sources of ballast water are;

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2. Characterisation of waste water
Oil tankers In many oil tankers, ballast water is carried in the cargo tanks after the vessel is unloaded to maintain the stability of the vessel. The ballast water will become contaminated by contact with the oil remaining in the cargo tanks and must be discharged to ballast water cleaning facilities before the vessel is loaded with the next cargo of oil. The waste water stream generated during the cleaning of storage tanks on oil tankers is also often classed as ballast water and may be treated in the same facilities. Tankers using Segregated Ballast Tanks (SBT) minimise the risk of contact between the oil and water by designating separate tanks which are only used for ballast water. Gravity Based Storage (GBS) platforms. Sea water is displaced from the storage cells as they are filled with produced oil, while sea water displaces oil from the cell when the oil is exported. Oil contaminates the water through a number of mechanisms including bulk mixing as the cells are filled and discharged, contact between the water and the oil coating the walls of the storage cell, residual oily water separating from the oil and through hydrocarbons dissolving and diffusing into the water phase. Ballast waters which have been in contact with hydrocarbons must be regarded as waste water and will usually require some treatment before they are suitable for discharge into the environment. Ballast waters can often be treated with relatively simple deoiling equipment. Residence times in storage tanks are generally quite long while shear forces are low which promotes the coalescence and separation of dispersed hydrocarbons. However ballast waters have a number of characteristics that do require special consideration.
0

Ballast waters are relatively cold in comparison with production waters with temperatures typically ranging from 5°C to 20°C. The hydrocarbon concentration can vary widely, ranging from clean water to slugs of hydrocarbons. Depending on the ballast water intake location and local environmental conditions, ballast water may contain significant quantities of suspended solids such as mud, sand, silt, organic and animal matter.

0

0

There are several cases of GBS structures which discharge displaced ballast water with hydrocarbon levels below 40 mg/l without any deoiling treatment. However provision should generally be made for some form of treatment of displaced GBS ballast waters to provide protection against accidental discharges of hydrocarbons. Passive methods such as buffer water ceils could be -used to provide suitable protection.

2.2.3.

Process water
Process water is secondary water generated as a result of the processing activities undertaken during the production of hydrocarbons. Process water can originate from a wide range of sources including;
0

Wash water used for crude oil desalting. Condensed vapours from glycol regeneration equipment. Water condensed during the compression of water saturated gas streams. Water associated with the injection of treatment chemicals.

The importance of the process water streams is dependent upon their magnitude relative to other water streams. In the case of gas platforms which often have low production rates of produced water, the process water can be a significant fraction of the waste water and may dominate the characteristics of the overall waste water stream.

2.2.4.

Drainage water
The drain system associated with E 8, P production sites collects water from a wide variety of sources.

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2. Characterisation of waste water
0

Closed drain systems will normally collect produced or process water, typically from the draining of process vessels. Open drain systems will typically collect drainage from surface area drainage and tundishes etc. The majority of the water stream in the open drains system will be intermittent run off from rain or hosing.

Drainage water will typically exhibit the following differences from either production or process water; Flow rates are intermittent, resulting from operations such as vessel draining, rain water, hosing and housekeeping activities. In addition to hydrocarbons and contaminants associated with the production stream, open drains water may contain other contaminants such as lubrication oils and greases from rotating equipment, diesel oil spillage and any other fluids or materials entering the drains by design or accident. Open drains waters will contain dissolved oxygen. Mixing of oxygenated drainage water with other waters may result in scaling or corrosion. Due to the relatively short contact time, hydrocarbons associated with rain water or wash down water are more likely to be dispersed rather than dissolved and thus potentially easier to treat. Information on typical drain system loads due to rainwater, hosing, deluge systems etc. and guidelines for the sizing and design of drainage systems are given in DEP 34.1 4.20.31 -Gen., “Drainage and Primary Treatment Facilities”.

2.2.5.

Other waters
Other waste water streams which may be discharged from E & P operations include cooling water, sewage effluent, waste cuttings and drilling mud. The treatment of these categories of waste waters is not addressed in this manual.

2.3.

CONTAMINANTS OF WASTE WATER
When considering waste water from E & P operations, the concentration of produced hydrocarbons is normally the focus of both the system design and environmental monitoring requirements. Produced hydrocarbons in waste waters are generally considered to encompass the non-polar mineral hydrocarbons present in the production well-stream. However in addition to the non-polar mineral hydrocarbons, waste water streams typically contain a wide range of contaminants, all of which may have a potential environmental impact. In line with the Group commitment to identification, management and minimisation of all waste streams, all the constituents of waste water streams should be identified and accounted for. It should be stressed that the relative importance of contaminants in discharge waters is strongly dependent upon the receiving environment, particularly the differential between the waste water and the receiving environment. An effective example of this is water salinity. Saline production waters may be relatively benign when discharged into a sea water environment, but may have a significant environmental impact when discharged into a fresh water environment.
A number of references are made to ASTM standard methods (American Society for Testing and Materials). These standards are readily available through most technical library services or can be requested from SIPM.

2.3.1.

Hydrocarbons derived from production streams
A typical waste water stream from an E & P operation will contain a wide variety of hydrocarbons derived from contact with the hydrocarbon production stream. The hydrocarbons in the waste water stream can be broadly grouped as dispersed, dissolved and polar hydrocarbons. To date, normally only the insoluble dispersed hydrocarbons have been considered when selecting deoiling equipment. Table 2.1 gives an indication of the relative contribution of each group of hydrocarbons in the waste waters discharged from a selection oil and gas production platforms in the North Sea.

2.3.1.l. Dispersed hydrocarbons
The treatment of waste water streams from many E & P operations is focused on the removal of
SlPM Deoilinji Mnurrtrl, EP 93-13/5, Rev 1.1, Nov 1993, File nrrnle = 2ClfAP.DOC

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2. Characterisation of waste water
dispersed hydrocarbons. Dispersed hydrocarbons are relatively insoluble in water and are present as discrete hydrocarbon droplets within the continuous water phase. Crude oil streams are usually largely composed of aliphatic hydrocarbons which have a low solubility in water. Thus the hydrocarbons in waste waters from oil production operations are typically present as dispersed hydrocarbons. One of the critical characteristics of dispersed hydrocarbons is the droplet size distribution of the dispersed hydrocarbon phase. The performance of most deoiling equipment will be ultimately limited by the smallest hydrocarbon droplet size that can be efficiently removed from the water stream. Droplets of dispersed hydrocarbons smaller than the minimum cut off size will not be removed. Droplet size distributions are discussed in more detail in section 2.4. The majority of deoiling equipment currently installed in E & P operations is only capable of removing dispersed hydrocarbons from waste waters.

2.3.1.2.Dissolved hydrocarbons
Some hydrocarbons are partially or completely soluble in the water phase. Table 2.2 lists the solubility of various pure hydrocarbons in fresh water at 15"C, illustrating that the lower molecular weight hydrocarbons and aromatic hydrocarbons have the highest solubility.
Table 2.2 Solubility of hydrocarbons in water (mgll at 15°C) ALKANES AROMATICS

Number of carbon atoms 1 2 3 4 5 6 7 8 9 10 11

Normal CnH2n+2 25 75 100 100 60 12 2.6 0.6 0.1 0.02

cycio

1 Ring

___-_--

Notes: 1. These solubilities are lor binary systems of a single hydrocarbonand fresh water and are only indicative for produced waters. Solubility levels in produced waters may be different due to lactors such as: a) The effect of the temperature and pressure in the reservoir where the water is in contact with the hydrocarbons. b) The presence of other species dissolved in the water phase such as inorganic salts and soluble organic species such as organic acids. c) Preferential partitioning of the hydrocarbons to the hydrocarbon phase when both hydrocarbonand water phases are present. 2. Source: Superseded SlPM Dehydration/Deoilingmanual, EP 89-0150

Crude oil streams are typically composed of higher molecular weight aliphatic and aromatic hydrocarbons which have a low solubility in water. Thus the dissolved oil content in the waste water from oil production operations is normally relatively low. This usually allows the waste water streams from crude oil operations to be treated to typical discharge standards by removal of the dispersed hydrocarbons alone. For gas production operations the dissolved oil content may be more significant. Gas hydrocarbon streams are composed of low molecular weight hydrocarbons and may also contain significant quantities of relatively soluble low molecular weight aromatic hydrocarbons such as benzene, toluene and xylene. The higher solubility of hydrocarbons associated with gas production is illustrated in Table 2.1. It can be seen that the typical level of dissolved hydrocarbons from the gas platforms is 482 mg/l, compared to only 6 mg/l for the oil platforms. For some gas processing installations, a significant quantity of the aromatic hydrocarbons in the waste
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2. Characterisation of waste water
water may be derived from the glycol regeneration system. Aromatic compounds are absorbed from the gas by the glycol in the gas dehydration contactor. Water and aromatics are then stripped from the glycol in the glycol regenerator, condensed from the regenerator overheads stream and the resulting watedaromatics mixture added to the waste water stream. The removal of dissolved hydrocarbons is more difficult than the relatively simple phase separation required for removal of dispersed hydrocarbons. With the exception of biological treatment systems, the majority of the deoiling equipment used in E 8 P operations is not designed for the reduction of the dissolved hydrocarbon content of waste water. Appendix J presents calculation methods for estimating the levels of dissolved hydrocarbons in water and discusses the effect of a number of external variables such as water salinity and temperature on the hydrocarbon solubility. Guidelines on the use of physical property predictive routines for modelling hydrocarbodwater systems within simulation packages (e.9. Pro/lI) are given in DEP 20.00.10.10-Gen., “Basic Data and Phase Behaviour Methods”.

2.3.1.3. Polar hydrocarbons
Waste water streams may contain a significant quantity of polar hydrocarbons such as organic acids which due to their polar characteristics are relatively soluble in water. It can be seen from Table 2.1 that in the waste water from oil platforms the concentration of polar hydrocarbons is nearly eight times greater than the combined dispersed and dissolved oil content.
It should be noted that the polar compounds are generally not reported as part of the hydrocarbon content of the water. The analysis procedures used to determine the hydrocarbon concentration in water often includes an adsorption step where the polar hydrocarbons are removed by an absorbent such as alumina or Florosil. The hydrocarbon content is then measured after the polar compounds have been removed.

In addition, most hydrocarbon analysis procedures require the extraction of the hydrocarbons from the water phase using a solvent. Polar hydrocarbons are not efficiently extracted by some solvents and are thus not included in the subsequent hydrocarbon analysis. However, some analysis methods (e.g. Total Organic Carbon) will measure polar compounds and will often indicate a hydrocarbon concentration far higher than that measured through conventional analysis methods. As for dissolved hydrocarbons, the majority of deoiling equipment currently installed in E & P operations is not capable of reducing the polar hydrocarbon content of waste water.

2.3.2.

Treatment chemicals
A wide variety of treatment chemicals may be present in waste water streams. Typical examples include corrosion inhibitor, scale inhibitor, demulsifiers, hydrate inhibitors, biocides, flotation aids etc. Other incidental chemicals may also be present such as detergents used for wash down purposes. The effect of such chemicals can be significant in the selection and design of deoiling equipment as; Many treatment chemicals are surface active and may stabilise small hydrocarbon droplets in the water phase. The corrosion inhibitors used in gas production operations and the demulsifiers used to assist oil dehydration can sometimes result in such stabilisation. The small droplets may be very difficult to separate with conventional deoiling equipment. Some treatment chemicals may be incompatible with other chemicals. Examples are demulsifier chemicals interfering with subsequent deoiling chemicals, or deoiling chemicals reacting with dilute polymers present in the water as a result of enhanced recovery schemes. Efforts should be made to reduce the use of treatment chemicals whenever possible on the basis of minimising both operating costs and the ingress of additional chemicals into the environment.

2.3.3.

Suspended solids
Suspended solids in waste water can originate from a number of sources such as formation solids, corrosion and erosion products, precipitates and as by-products of biological processes within the process facilities. Solids may also originate from process equipment such as the degradation of molecular sieve or packing materials. The treatment and discharge of drilling cuttings and drilling mud is

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2. Characterisation of waste water
not addressed in this manual. From an environmental viewpoint, suspended solids may have a number of potential impacts, including; Some solids may be toxic themselves, contain toxic elements or have radioactive constituents.
0

Solids may trap or collect other contaminants. For example, solid particles may be oleophilic, attracting and trapping hydrocarbons which will be discharged with the solids. Discharged solids may accumulate as mud or silt in the local environment.

0

Discharged solids may result in turbidity in receiving environments with poor dispersion characteristics. Such turbidity may have an environmental impact as well as being undesirable visual pollution.

Suspended solids may have a significant impact on the design of deoiling equipment. Erosion and the effects of solids accumulation in deoiling equipment must be considered. In some cases equipment will be specifically designed to allow the accumulation of solids which can be periodically removed. The "Sand Wash Design Manual" EP 93-1270, due to be issued in the 4th quarter of 1993, contains additional information on topics including: The transportation, deposition and accumulation of solids in production systems. The design of equipment and jetting systems for the collection and removal of solids. The handling and disposal of solids contaminated with hydrocarbons.

2.3.4.

Heavy metals
The presence of heavy metals in waste waters can be of concern due to their potential toxicity and propensity for bio-accumulation. However not all heavy metals are regarded as dangerous. Table 2.3 gives a guide to the relative toxicity of a range of heavy metals and inorganic compounds.
Table 2.3 Relative toxicity of heavy metals and inorganic compounds Heavy metal or Environmental Heavy metal or inorganic Ranking inorganic compound compound Aluminium 1 Manganese Mercury Barium 1 Molybdenum Boron 1 Nickel Cadmium 3 Calcium Phosphorus 1 Potassium Chromium 3 Cobalt Silicon 1 Copper Sodium 3 Iron Strontium 1 Lead Sulphate 3 Lithium Vanadium 1 Magnesium Zinc 1 Rankings: 1 ... 1 critical 2 ... Toxic, but rare or having low solubility 3 ... Highly toxic and relatively accessibleEnvironmental Ranking
1 3

2
3 1 1 1 1 1 1

2
3

Source: Shell Expro's Wastes, 1989, Safety and environmental affairs department, ref

2.3.5.

Salinity
The salinity of water is typically expressed as the concentration of Total Dissolved Solids (TDS), indicating the quantity of dissolved inorganic salts present in the water. The salinity of the waste water should be considered for the following reasons;

For surface disposal, the salinity of the discharge water should not be significantly different from the salinity of the receiving environment. This should encompass both the discharge of saline water into fresh waters and the discharge of fresh water into saline waters (e.g. inshore).
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~

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2. Characterisation of waste water
Salinity affects the density of the water which will in turn influence the design of gravity based separation equipment and the dispersion characteristics of disposed waste water. Changes in the composition or process conditions of saline waters (e.g. temperature changes) may lead to the precipitation of inorganic salts and scale formation. The salinity and aeration of the water will add to the corrosion potential of the water stream, influencing the selection of materials for process equipment.

2.3.6.

pH
The pH determination of water is a relatively reliable indication of its acidic or alkaline tendency. However it is not a measure of the actual acidity or alkalinity in a water sample. ASTM D 1293-78 discusses the measurement of pH while ASTM D 1067 discusses the measurement of actual acidity or alkalinity. The pH of the waste water is subject to regulation in some countries which typically require the pH of discharged waste waters to be between 5.5 and 9.0 Alkaline waste waters with a pH in the range of 8-10 may react with components of the hydrocarbon stream to form surfactant type chemicals. These surfactants may assist in stabilising emulsions.

2.3.7.

Hardness
Hardness in water is generally caused by the presence of calcium and magnesium ions, though any polyvalent cation can contribute to hardness. Hardness in water can result in scale formation in process equipment. The release of dissolved CO, during depressurisation may also alter the hardness characteristics of water.

2.3.8.

Thermal contamination
Although not strictly a contaminant, the temperature of discharged waste waters may have an impact on the environment. The impact will be dependent on factors such as the temperature differential to the receiving environment and the physical extent of the temperature gradient. The temperature will also affect the density and viscosity of the waste water. These variations must be accounted for in the design of waste water treatment equipment and when modelling the dispersion characteristics of waste water discharges. The temperature of waste water discharges may be subject to regulation, especially in the case of discharges into inland water bodies such as rivers and lakes.

2.3.9.

Dissolved oxygen
From an engineering standpoint, the presence of oxygen in a water stream is very important due to its potential role in the corrosion of process piping and equipment and in the resultant corrosion products in effluent waters. Produced waters do not normally contain any dissolved oxygen, however oxygen may be introduced into the process through open equipment and tanks or through the use of aerated waters such as fresh water used for desalting. From an environmental viewpoint, the levels of oxygen in discharged water can have a significant impact on the receiving environment. Discharge of oxygen free water into surface waters may result in an oxygen deficiency in the local aquatic environment. Some countries have regulations governing the quantity of dissolved oxygen that must be available in waste water discharges. Conversely, the presence of contaminants in the waste water can affect the level of dissolved oxygen in the receiving environment by consuming oxygen through biological and/or chemical oxidation of the contaminants. The oxygen demand of a waste water stream is an indication of the oxygen depletion that may be imposed on the receiving environment. Oxygen demand is measured and expressed in several different ways.

2.3.9.1.

Biological oxygen demand (BOD)
The biological oxygen demand is defined as the quantity of oxygen (expressed in mg/l) consumed by micro-organisms degrading organic material under aerobic conditions. An example is the test method from the American Public Health Association (APHA), "Standard methods for the examination of water and waste water", p483, 15th ed.

SIPM flroilinl: Monual. EP 93-1315. Rev 1.1. Nov 1993. File

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2. Characterisation of waste water
Complete biological oxidation of all the contaminants present in waste waters can potentially take from 20 to 100 days. As this time period is too long for analytical purposes a shorter test, termed the “five day BOD” (BOD,), which measures the amount of oxygen consumed in the first 5 days of biological oxidation at 20°C is commonly used. BOD is an important guide to the amount of micro-organic activity that can be supported by the organic elements present in the waste water. Discharging waters with a high BOD may result in an oxygen deficiency in the local aquatic environment.

2.3.9.2.

Chemical oxygen demand (COD)
The chemical oxygen demand is defined as the quantity of oxygen (expressed in mg/l) consumed by chemical oxidation of organic and inorganic material in waste water, corrected for the presence of chlorides. The COD test was developed to give a faster estimate of the oxygen demand than the BOD procedure. Although theoretically the COD should equal the ultimate BOD, in practice this is not always the case for waste waters. However it is oflen possible to develop a relationship between COD and BOD which allows the COD to be used as an indicator for controlling BOD. An example of a COD test method is ASTM D-1252-78 which is based on the reduction of a dichromate solution under specified conditions. However this method is not suitable for waste waters containing more than 1 g/l of chloride ions, which precludes its use for many saline produced waters.

2.3.9.3.

Total oxygen demand (TOD)
The total oxygen demand is the amount of oxygen required to convert the elements present in waste water contaminants to their most stable oxidised forms. An example of a TOD test method is ASTM D 3250-77 which measures the TOD by oxidation of the water stream at 900°C. The TOD method can be used for brackish waters and brines.

2.3.1 0. Organic carbon
A number of measurements of the quantity of carbon in a water sample are possible. When a sample is homogenised such that both inorganic and organic carbon is measured, the result is known as the Total Carbon (TC). Eliminating the inorganic carbon response from the measurement gives the Total Organic Carbon (TOC). When particulate carbon is removed from the sample, the net measurement is the Dissolved Carbon (DC), or if the inorganic carbon response is eliminated, the Dissolved Organic Carbon (DOC). ASTM D 2579-78 discusses test methods for measuring total and organic carbon and references additional information relating the TOC to other measures of water quality such as BOD and COD.
It should be noted that carbon measurement encompasses all forms of carbon including polar hydrocarbons, carbonates and other forms of carbon which are not normally classified as part of the “mineral hydrocarbon” content of a water stream.

2.4.

DROPLET SIZE DISTRIBUTIONS
The droplet size distribution is one of the most crucial characteristics governing the removal of suspended solids or hydrocarbon droplets from water. Many designs of deoiling equipment have a limit on the smallest hydrocarbon droplet size that can be efficiently removed from the water stream. Figure 2.1 illustrates a typical droplet size distribution curve in terms of hydrocarbon volume. The size distribution is typically categorised by a mean droplet size, however the mean droplet size must always be defined on an associated basis, e.g. numerical mean, volume/weight mean, surface area mean etc. When reporting mean droplet sizes the basis for the mean should always be clearly stated. A recommended method for expressing mean droplet sizes is the mean volume droplet size D(v,o.5). This is defined as the droplet diameter such that half the volume of hydrocarbons present is encompassed in smaller droplets and half the volume is contained in larger droplets. Graphically, as illustrated in Figure 2.1, the mean volume droplet diameter divides the volume distribution such that half the area under the curve is on either side of the mean, in this case the mean volume diameter being 26.6 pm. The volume based mean droplet diameter can be more readily determined by plotting the cumulative percentage volume as indicated in Figure 2.2. The numerical mean, defining the point where half the number of droplets are either larger or smaller is oflen not as useful for indicating the distribution of dispersed hydrocarbons. The volume o f hydrocarbon contained in the smaller droplets may be insignificant when compared to the larger droplets. For

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2. Characterisation of waste water
example, a single 50pm droplet contains 1000 times the volume of a 5pm droplet. The numerical mean for the distribution illustrated in Figure 2.1 was separately determined to be 2.3 pm, significantly lower than the volume based mean. Thus, even though half the number of droplets are smaller than 2.3 pm, from Figure 2.2 we can see that volume of hydrocarbons contained in these droplets is less than 5% of the total hydrocarbon droplet volume.

10

9
8

0.1

1

10
Particle size (urn)

100

1000

Figure 2.1 Example of a particle or droplet size distribution

100

90 80
70

60

50
40

30

20
10

0
0.1
1

10
Particle size (urn)

100

1000

Figure 2.2 Cumulative volume based droplet size diameter

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2. Characterisation of waste water

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3.Emulsions

3.1. 3.1.1.

DEFINITIONS General
An emulsion can be simply defined as a dispersion of one immiscible liquid in another. By this definition, any mixture of two liquid phases is an emulsion, regardless of whether the dispersion of the phases is stable or unstable. In practice, emulsions generally have some degree of stability that prevents them immediately separating into non-dispersed phases. However stability can range from extremely stable emulsions requiring special treatment to “break”, to relatively unstable emulsions which will separate in a finite time under suitable conditions. Thus the term “emulsion” applies to most dispersions of hydrocarbons in water encountered in E & P operations, from tight, stabilised emulsions to relatively unstable mixtures. Due to the relatively low volume of hydrocarbons compared to the volume of water, the oil-in-water emulsions encountered in deoiling processes have relatively simple behaviour. The bulk of the emulsion is formed by the continuous water phase and thus physical parameters such as viscosity are relatively well defined. Emulsion characteristics for the water-in-oil emulsions encountered in oil processing may be significantly more complex involving problems such as significant quantities of evolved gas, high viscosity and phase inversions. For a more detailed discussion of water-in-oil emulsions the user is referred to the emulsion references listed in the bibliography of this manual and the SlPM Dehydration/Deoiling manual.

3.1 2.

Distribution of phases
Emulsions are characterised by a distribution of two liquid phases. The phase present in the form of discrete droplets is known as the dispersed or internal phase, while the phase which forms the matrix in which the droplets are suspended is known as the continuous or external phase. The two emulsions typically encountered in oil and gas production operations are; Hydrocarbons droplets dispersed in a continuous water phase, referred to as an oil-in-water, o/w or reverse emulsion. Water droplets dispersed in a continuous hydrocarbon phase, referred to as a water-in-oil, w/o or normal emulsion. More complex emulsions can occur, sljch as an oil-in-water emulsion forming droplets within an oil phase, forming an oil-in-water-in-oil emulsion. However such complex emulsions are considered to be rare. The deoiling processes covered in this manual are designed for the first type of emulsion, hydrocarbon droplets dispersed in a continuous water phase.

3.1.3.

Stability
Depending on how readily the phases can be separated, emulsions can be classed as unstable or stable. As will be discussed later, simple emulsions are by nature unstable and in the absence of external factors an emulsion will generally disengage into separate phases. However, in practice most emulsions are not simple and are often stabilised by the presence of some form of emulsion stabiliser. The emulsion stabiliser prevents dispersed droplets from coalescing or slows the coalescence to an rate that may be unacceptable for processing activities.

3.1.4.

Size distributions
Emulsions can be broadly characterised by the size of the droplets of the dispersed phase. Primary emulsions have a droplet diameter typically larger than 100 pm. Due to the large droplet size such emulsions are usually relatively easy to separate. Secondary emulsions have a droplet diameter typically between 0.5 pm and 50 pm. This encompasses many oil-in-water emulsions encountered in E & P waste water treatment operations.

3. Emulsions
Micro emulsions have droplet sizes in the order of 0.01 pm to 0.1 pm and are optically transparent.

3.2. 3.2.1.

FORMATION OF EMULSIONS Formation locations
To form an emulsion requires an input of shear energy into a system containing two immiscible liquids. Typical locations where this can occur are; Downhole perforations Gravel packs Subsurface pumps High GOR tubing flow including gas lift. Chokes Manifolds Pumps Throttling control valves Typically, the higher the degree of energy input, the smaller the droplet size distribution of the dispersed phase. For example, control valves, where the fluids undergo a large pressure drop in a very short time, are capable of producing very fine emulsions. Thus the distribution of droplet sizes in an emulsion is dependent on the physical properties of the hydrocarbons and water, and on the amount of shear that the emulsion has been subjected to (its shear history).

3.2.2.

Mixing energy and droplet size distributions
Prediction of the droplet size distribution in an emulsion is extremely difficult. A relationship between maximum droplet size in a non-stabilised emulsion and the mixing energy exerted on the system has been developed by Hinze and is presented in Appendix A. This relationship can be used as a guide to the relative size of droplets that may be generated by the imposition of different mixing energies on a nonstabilised emulsion. In its normal form the Hinze relationship does not account for a number of important factors, such as the presence of emulsion stabilisers or the evolution of free gas, which will have a significant impact on the droplet size distribution achieved in practice. However these influences could potentially be accounted for by empirical modification of the basic equation form.

3.3. 3.3.1.

STABILEATION OF EMULSIONS Immiscible liquids
Liquids are miscible when there is some form of attraction between the component molecules of the two phases. The physical structure of a water molecule is such that it has an uneven distribution of electric charge across the molecule. As this effectively gives water molecules areas of different electrical charge it is referred to as a polar molecule. As water is a polar molecule, it will have an affinity for other polar molecules, thus allowing other polar compounds to dissolve in water. Aromatic hydrocarbons (e.g. benzene, toluene etc.) have some polar characteristics, making them partially soluble in water.

As a contrast, the majority of hydrocarbons associated with oil and gas production are non-polar. As such there is little attraction between the water molecules and the hydrocarbon molecules and the two liquids are regarded as insoluble or immiscible.
In practice, there will usually be some limited solubility between even immiscible phases. Solubility of hydrocarbons in water is discussed in more detail in Chapter 9.2.

3.3.2.

Surface tension
Molecules within a liquid or gas are subject to short range attractive (van der Waal) forces. In the bulk of the liquid, each molecule is surrounded on all sides by other molecules, thus the attractive forces are relatively evenly distributed.

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3. Emulsions
However, the molecules at the interface between a liquid and a gas, not being completely surrounded by other liquid molecules, are subject to an unbalanced attraction which has the net result of an attractive force directed inward, normal to the surface. This effect is illustrated in Figure 3.1. The smaller the surface, the lower the free energy associated with the surface, thus the surface of the liquid has a tendency to contract. This effect is apparent as surface tension. Surface tension can be defined and measured as the work required to generate an additional unit of surface area.
~

.--- _ _ -- - z ~ L -- = ~ : - - G - q~ X ~ ~z--~~g~~---~~~~--~~ggz .....................
: ~

Air

HIXtZWIP

3.3.3.

Interfacial tension
When two immiscible liquids are placed in contact, an interface between the two phases will result as shown in Figure 3.2. Unlike a gashquid interface, there will be some attraction between the molecules of the two liquids due to the relatively close proximity of molecules at the interface. However, the attraction will be stronger to the molecules of the same type in the bulk of the liquid, leading to an imbalance of forces and the creation of an interfacial tension. This effect will be present in both phases. Hence it is to be expected that the value of the interfacial tension will lie between the individual surface tensions of the two phases. Any system will attempt to move towards a state of lower energy. The forces present at the interface between the two phases represent a form of energy and the system will move to minimise this energy by the following means. As a sphere has the lowest surface area per unit volume, in the absence of other forces a droplet of the dispersed phase will adopt a spherical shape.
2:

For a given volume of liquid, one large droplet will have less total interfacial area than two smaller droplets. As the interfacial area is associated with energy (interfacial tension), smaller droplets will tend to coalesce into larger droplets to minimise the energy associated with the interfacial tension.

Thus, the presence of interfacial tension will cause the dispersed droplets in an emulsion to naturally coalesce. The greater the interfacial tension, the greater the tendency for the droplets to coalesce. However, in practice other influences are commonly present that will act to stabilise the emulsion and inhibit coalescence.

3.3.4.

Contact angles and wetting of solids
The attractive forces between liquid and solid phases gives rise to the concept of contact angles and the “wetability” of a solid. For example, a hydrocarbon with a strong attraction to a solid phase will tend to spread out into a film, “wetting” the solid, while a hydrocarbon with a weak attraction will tend to bead and the solid may be considered “water wetted. The wetability of a system can be related to the contact angle 0. For an oil-water-solid system, 0 is defined as the angle, measured through the aqueous phase, that is formed at the junction of the three phases. The contact angle can be related to the interfacial tensions between the phases by Young’s equation;
Y(w/o) cos 0 = Y(d0) - Y(s/w)

Eq. 3.1

Where:

y = (w/o)= (do) = (s/w) =

interfacial tension (mN/m or dyne/cm) water/oil interface solid/oil interface solid/water interface
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SlPM Duoilinx Mioiirrrl. EP 93-131s. Rev 1.1, Nov 1993. File IIirnw = 3CfIAP.DOC

3. Emulsions
The solid is completely water wetted if 0 = 0 and only partially wetted otherwise. In practice, contact angles of 0 < 90" are often considered to represent "water wetting" and values of 0 > 90" to represent "non water wetting". This assignment is rather arbitrary as it is based on correlation with the visual appearance of droplets on surfaces. Wetting considerations can play an role in the stabilising of emulsions. Solids may give additional mechanical strength to an interface, supporting an emulsified state. The most stable emulsions will occur when 0 = 90" as the solids will be supported in the interface by both phases. Combining Young's equation with oriented wedge theory (ref 1.08.1 .a) predicts that fine solids which are water wetted will be better at stabilising an oil-in-water emulsion while solids which are oil wetted will be better at stabilising a water-in-oil emulsion.

3.3.5.

Emulsion stabilisers
Factors affecting emulsion stability By definition, the stability of an emulsion is a time dependant characteristic. An emulsion that takes several days to disengage into separate phases is unstable as coalescence is slowly occurring, however for practical processing purposes, such an emulsion is considered stable. An emulsion may be stabilised by one or more of the following factors.

3.3.5.1.

Low interfacial tension. A low interfacial tension means there is less driving force to minimise interfacial area by coalescence and it is energetically easier to maintain a dispersed state. Many emulsion stabilising agents such as surfactants act by lowering the interfacial tension.
Mechanically strong interface film. A strong interfacial film acts as a barrier to coalescence. The mechanical strength of a film may be enhanced by the absorption of solids or close packed surfactant molecules.
0

Electric double layer repulsion. The repulsion between similarly charged droplets acts to prevent droplet collision, agglomeration and coalescence. Small volume of dispersed phase. Reduces the probability of collisions between dispersed droplets.

These factors are examined in more detail in the following discussions.

3.3.5.2. Lowering interfacial tension - Surfactants
Surfactants are surface active chemicals which alter the characteristics of the interface between liquid phases. Surfactants are generally characterised by having two distinct sections of the molecule, a hydrophilic (water loving) section and an oleophilic (oil loving) section. Each section has an affinity to one of the two phases, allowing the surfactant to locate itself at the interface between the phases where it can exert a stabilising effect on the emulsion.

--------- - _ _ _ --_--_ -_ -_- _ _ _-_---- - - - - - _ -_ _

______

_

: I : -

-z -_ _z -r -_ -_ _ _ -_ -_ -_ _-Figure 3.3 illustrates how a surfactant behaves in an oil~ i_ i _-___ _- _ _ __ _ _ _ ---- -______-_ ___ --_ _-__ in-water emulsion. The oleophilic end of the molecule ----------------HlXRMP aligns itself towards the hydrocarbon phase while the Figure 3.3 hydrophilic end is orientated towards the water phase, Surfactant stabilising an forming a protective "skin" around the droplet. The oil-in-water emulsion surrounding water phase only "sees" the hydrophilic end of the surfactant, while the hydrocarbon droplet only "sees" the oleophilic end. This reduces the interfacial tension between the two phases, hindering the coalescence process and stabilising the emulsion. The presence of the surfactant molecule at the interface may also increase the interfacial viscosity, providing a mechanical resistance to droplet coalescence.

_---__

_----_ _-___ _--

Surfactants are classified as either anionic, cationic or non-ionic according to the nature of the hydrophilic end of the molecule. Examples of these surfactants are given in Table 3.1 and discussed below. Anionic surfactants are typically oils and alcohols, organic amine-fatty acid soaps and sulphated aliphatic and aromatic compounds where the hydrophilic section is negatively charged. The best
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3. Emulsions
known example are common soaps. Cationic surfactants are characterised by the hydrophilic section being positively charged, such as quaternary ammonium salts. Non-ionic surfactants are organic molecules which do not ionise in solution. The majority of demulsifying chemicals used in the oil industry to assist the destabilisation of water-in-oil emulsion are of the non-ionic type such as esters containing water soluble groups which are polymers of either ethylene and/or polypropylene oxide.
Table 3.1 Classification of surfactants Class Anionic Na stearate Examples

Na dodecyl sulphate
Na dodecyl benzene sulfonate Cationic Laurylamine hydrochloride Cetyl trimethylammonium bromide Non-ionic
Source:

Polyoxyethylene alcohol Alkylphenol ethoxylate

Em( ions. Fundamentals and applications in the petroleum industw, edited by Schamm, L.L., Ref.1.OB.1 .a

Oil-in-water emulsions may also be stabilised by a high pH (8-10) in the water phase. The alkaline components of the water may react with organic components to form soap like molecules. These molecules may then act as surfactants and stabilise emulsions. Some treatment chemicals may also act as emulsion stabilisers. Corrosion inhibitors are often designed to be highly surface active and as a consequence may be very effective emulsifiers. Overdosing of demulsifiers (treatment chemicals designed to destabilise and promote the coalescence of a water-in-oil emulsion) may result in stabilisation of an oil-in-water emulsion in the separated water phase.

3.3.5.3.

Electrical charge The droplets of the dispersed phase may carry an electric charge. This charge could be a surface characteristic of the dispersed phase, but is most often associated with the presence of ionic surfactants at the droplet interface. Ionic surfactants arrange themselves with the charged hydrophilic end of the surfactant molecule facing into the continuous water phase. This gives the external surface of the hydrocarbon droplet an external charge, the polarity of the charge being dependent upon the ionic characteristics of the surfactant. In most cases, the external surface of an oil-in-water emulsion tends to be negatively charged. However, the presence of an external charge layer on the hydrocarbon droplet causes a further realignment of the ions within the water phase. Positive ions will be attracted to the negative surface charge, forming a diffuse positively charged region around the droplet. This is referred to as the double layer effect. The net result in an emulsion is that the dispersed droplets will often carry an electrical charge and will repel each other, reducing the probability of droplets colliding and coalescing. The double layer effect is usually more effective at stabilising oil-in-water emulsions than water-in-oil emulsions. The continuous water phase in an oil-in-water emulsion has many small, mobile ions in solution which readily accumulate to form an effective double layer around the dispersed hydrocarbon droplets. Continuous hydrocarbon phases do not contain the same small mobile ions and are thus less effective at such charge based stabilisation.

3.3.5.4. Solids
The presence of fine solids may have an influence on the stability of an emulsion by accumulating at the interface between the phases. Such solids may include;

SIPM Droilinl: MIIIIIIIII, EP 93-13l.~.Rev 1.1. NIIV 1993. File mime = 3CIiAP.DOC

P q e 3-5

3. Emulsions
Formation solids Insoluble asphaltenes and resins Precipitated scales e.g. calcium carbonate, calcium sulphate, barium sulphate. Corrosion products e.g. iron oxides, iron sulphides Wax crystals To have a significant influence the solids should be small compared with the dispersed droplet size, allowing the solid particles to be absorbed into the interface between the liquid phases. The influence of solids on coalescence is dependant on a variety of factors such as the surface characteristics of the solids and which phase they are preferentially wetted by. In general, particles which are wetted by the water phase will tend to stabilise an oil-in-water emulsion, while conversely, solids which are preferentially wetted by the hydrocarbon phase will tend to stabilise water-in-oil emulsions. The wettability of solids is discussed in section 3.3.4. However the mechanisms by which solids affect emulsions are complex and exceptions to these general rules can often occur. Solids may influence emulsion stability through other paths such as forming bridges between droplets or influencing the surface charge characteristics of the dispersed droplets.

3.3.5.5.

Low hydrocarbon concentration, fine size dispersions
In order for a dispersed phase to coalesce there must be contact between the dispersed droplets. An oil-in-water emulsion with a low hydrocarbon concentration and small droplet size will have a statistically low probability of contact between droplets and thus will have a relatively slow coalescence rate. Thus, although the hydrocarbon concentration and droplet size distribution are not true emulsion stabilisers, a dilute, disperse oil-in-water emulsion typical of the feed to a deoiling system will effectively appear more stable than a more concentrated emulsion as the process of coalescence will be slower.

3.4.
3.4.1.

TREATMENT OF EMULSIONS General
A stable emulsion may form if three conditions are satisfied. Presence of two immiscible liquids. Presence of an emulsion stabilising agent. Energy is put into the system e.g. agitation or pressure drop. However these conditions are infinitely variable and thus there is an infinite variety of emulsions which can be produced. To enable a stabilised emulsion to coalesce ("break" an emulsion) the following conditions must be fulfilled. The stabilising mechanism must be overcome to allow the droplets to coalesce upon collision. The dispersed droplets must collide. Emulsion treating techniques operate by ensuring these conditions are met. However due to the wide variety in the types and characteristics of emulsions, the particular combination of techniques used to break an emulsion must usually be determined on a site specific basis. The emulsion breaking techniques discussed in this Deoiling Manual are focused on oil-in-water emulsions. For discussions of emulsion treatment methods for water-in-oil emulsions the user is referred to the dehydration sections of the current SIPM Dehydration/Deoiling Manual (EP 89-0150) or the emulsion references listed in the Bibliography. Some information on the breaking of very stable sludge type emulsions is given in section 4.5.3.

3.4.2.

Emulsion breaking chemicals
An emulsion breaker is typically a surface active agent which migrates through the continuous phase to the hydrocarbon/water interface. At the interface the emulsion breaker reverses or neutralises the effect of the emulsion stabiliser. Emulsion breakers for water-in-oil emulsions are commonly referred to as dernulsifiers while emulsion breakers for oil-in-water emulsions are commonly referred to as deoilers.

It should be recognised that the behaviour of demulsifiers and deoilers may not be complimentary. For
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3. Emulsions
example, a demulsifiers added to crude oil to assist in its dehydration may result in the formation of a stable oil-in-water emulsion in the separated water, especially if the demulsifier is overdosed. 3.4.2.1. Composition of deoilers Because the emulsion stabilising agents will be different for each application, each deoiler has to be tailored to obtain the optimum results. A typical deoiler consists of a number of chemicals designed to reverse the effect of each emulsion stabiliser: Surfactant stabilisation can be overcome by reversing or hindering the oleophilic/hydrophilic nature of the surfactant. Stabilisation by solids can be overcome by altering the surface characteristics of the solids, allowing the solids to disperse from the interface into one of the phases. Electrical charge stabilisation can be overcome by allowing the charge to be redistributed or hidden. For oil-in-water emulsions the emulsion stabilising surfactants tend to be anionic in nature. Thus many deoiler chemicals typically contain mixtures of cationic surface agents and polymers. The cationic agents neutralise the anionic characteristics of the emulsifier, overcoming the electrical repulsion of the hydrocarbon droplets. Deoilers are typically supplied as 25-50% solutions of the active chemicals dissolved in a water soluble solvent. 3.4.2.2. Testing and selection of deoilers Testing of deoiling chemicals in laboratory or bottle type tests presents a number of problems such as the relatively low hydrocarbon concentrations, the time dependant nature of the emulsion size distribution and emulsion stability and the difficulty in obtaining and preserving representative samples of a dilute emulsion. Because of these problems, laboratory or bottle type tests should only be used for the screening of a range of deoilers. The final performance and optimum dosage rate for a deoiler should then be confirmed through field trials with the deoiling equipment. In addition to the performance of the deoiler in destabilising the oil-in-water emulsion, the selection of the deoiler should also consider the following; Temperature. The deoiler should work satisfactorily over the full range of process temperatures that may be encountered in the effluent treatment equipment. Although higher temperatures are generally favourable for destabilisation of emulsions, the deoiler should remain stable and effective at these temperatures. Similarly, the deoiler should also operate efficiently when the temperature is at a minimum such as in winter. Treatment chemicals. The interaction of the deoiler with other chemicals should be considered. Some treatment chemicals may hinder the performance of the deoiler, leading to excessive deoiler consumption. If demulsifiers are used in the upstream processing for destabilisation of water-in-oil emulsions, the demulsifier and deoiler should be compatible. Environmental impact. Being injected into the effluent stream, a proportion of the deoiling chemicals will be discharged into the environment with the treated water. As such the deoiler and its carrier fluid should be suitable for release into the environment. The performance of a deoiler may not be constant with time. Changes in the characteristics of the production well stream or the upstream processing operations may require the selection or dosage rate of the deoiler to be investigated. Similarly, if significant increases in deoiler consumption are required to maintain satisfactorily performance, the selection and dosage rate of the deoiler should be reviewed. 3.4.2.3. Deoiler injection location and dosage rates Deoiler chemicals should typically be injected as soon as possible afler the bulk oil and water separation stage as the presence of the deoiler in the water stream should help to minimise subsequent emulsification and allows the maximum time for coalescence. For example, injection upstream of a water level control valve would ensure good mixing of the deoiler and water stream and help to prevent the
SlPM Droilinji Miinucil. EP 93-1315, Rev 1.1, Nov 199.7, File niinie = 3CliAP.DOC

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3. Emulsions
formation of a stable emulsion. Deoiler injection rates should be controlled to ensure correct dosage. This may preclude injecting at location where the water flow is intermittent. Dosage rates are typically of the order of 5 mg/l. The efficiency of a deoiler may be reduced though overdosing and in some cases may even result in stabilisation of the emulsion. The dosage rate should be optimised on the basis of field trials.

3.4.3.

Other methods of emulsion treatment
In addition to the use of special deoiling chemicals there are other potential methods which may be used to assist in destabilising an oil-in-water emulsion.

3.4.3.1. Thermal treatment
The addition of heat to an emulsion usually assists the resolution of the emulsion into separate phases. In most cases, the addition of heat alone to a system is not sufficient to break an emulsion and thermal treatment is used in combination with emulsion breaking chemicals. These techniques are commonly required for the treatment of water-in-oil emulsions, but are not normally economic for the treatment of large water streams containing a relatively small quantity of hydrocarbons. However the overall system design should consider methods of maximising the process temperatures where the separation of emulsions is required.

3.4.3.2. Acidification
As noted in section 3.3.5.2, a high pH in the water phase can stabilise the emulsion by reaction of the alkaline components in the water with the hydrocarbons. The addition of acids to the system may counter this effect and result in better deoiling performance.
Changes to the water pH may also influence the surface charge of the dispersed droplets. Reducing electrical charge would reduce the repulsive forces between the dispersed droplets and thus assist coalescence.

3.4.3.3.Addition of divalent cations
Soap-like surfactants stabilising oil-in-water emulsions typically contain univalent cations which ensure their solubility in water. Addition of divalent cations (such as Ca++,effectively making the water "hard") may precipitate these soaps as insoluble salts, removing their ability to stabilise the emulsion.

3.4.3.4. Electrical treatment
The use of electrostatic fields is often used to promote the separation of water-in-oil emulsions. However due to the conductivity of water this technique cannot be applied to oil-in-water emulsions.

.

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4. Water disposal

4.1.

GENERAL
The water produced as a result of production operations needs to be disposed in a responsible and environmentally acceptable manner. There are three major forms of water disposal. Surface disposal Water injection Disposal injection Surface disposal is generally subject to regulation and is a potential source of environmental pollution. Regulatory restrictions, as well as a Group commitment to minimising discharges into the environment, will see subsurface disposal techniques become more important in future operations. The different types of water disposal methods often set the performance criteria required from deoiling equipment, such as the regulatory limits on hydrocarbon levels for surface water disposal or reservoir imposed limitations on solids and hydrocarbon content imposed for subsurface disposal.

4.2.
4.2.1.

SURFACE DISPOSAL Regulatory discharge limitations
Surface disposal of water involves the discharge of treated effluent water into the surface environment. The most common surface disposal locations are;
0 0
0

Rivers Lakes Coastal waters Offshore waters

Because of the potential impact on the environment, the discharge of effluent waters is normally governed by regulatory limits set by national or regional authorities. Table 4.1 indicates the allowable hydrocarbon discharge concentrations for coastal and inland discharges while Table 4.2 lists the allowable levels for offshore discharges.
Table 4.1 National coastal and inland oil-in-water limits

Country Belgium Denmark Nigeria USA Venezuela

Maximum allowable oil content (mgll) 20 10

Average monthly oil content (mgll)

____42 20

----_
_--_Average oil content (mg/l)

_____
20 29

Country Belgium Denmark France Italy Malaysia Nigeria Norway Portugal Switzerland Germany

Maximum oil content (mqh)

5 5 20

1 0 1 0 5-20 5-20

lo

1 0
5

_____

-____ -____ ----_____ .---.

____-____ __-__ -----

representsnew 1993 targets. Nigerian figures are proposed, not yet

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4. Water disposal
Table 4.2 National offshore oil-in-water limits

OFFSHORE
Country Abu Dhabi Australia (Victoria) Canada Denmark France India Malaysia Netherlands Nigeria Nowav PARCOM Spain United Kingdom USA Maximum oil content (mgn)

__---

15 50 50
20 40

EWPt

15

40 75 40 No more than 4% >loo' 100 No more than 4% >loo' 42

_-_-_

3. USA figure is new

29

* 4% of samples taken

The discharge limits for territorial seas and offshore continental shelf installations in the USA were lowered in January 1993. The new limits are an average of 29 mg/l per month with a maximum of 42 mg/l per day. Both new and existing installations will be required to satisfy the more stringent regulations. In general the regulations covering water discharges are most stringent for inland locations, with the regulations often controlling a wide variety of substances including both dispersed and dissolved hydrocarbons, heavy metals, biological oxygen demand etc. In contrast, regulations covering offshore effluent discharges are less coherent. Limits have typically been set on the basis of expected performance levels of available deoiling equipment and not on environmental impact considerations.

It should be noted that regulations from different countries or within the same country often have considerable variation in areas such as defining which components are considered hydrocarbons, whether dissolved and polar hydrocarbons are included and which hydrocarbon analysis method should be used.
A good example is the gravimetric analysis method required by some regulations tends to measure a lower hydrocarbon content than the infrared analysis method required by other regulations. Some regulations allow gas sparging of the sample which strips volatile hydrocarbons from the sample. Due to these variations, a limit set or measured under one set of regulations is not always directly comparable to a limit under a different set of regulations.

Table 4.3 gives a qualitative guide to the surface appearance of water containing small quantities of hydrocarbons. Although each hydrocarbon and water combination will be different, for this particular oil/water combination it is apparent that it is difficult to visually detect low levels of hydrocarbons.

Oil concentration (mgll)

Effect on surface of water sample Not visible Silvery sheen Traces of colour Bright colour Dull colour Dark colour
I

0 to 30 30 to 60 60 to 100 > 120
> 400 > 800

Source:

SlPM Dehydration/Deoilingmanual EP 89-0150.

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4. Water disposal
4.2.2. Setting of environmental discharge standards
In addition to regulatory limitations, the treatment of waste water streams should be governed by local environmental considerations. An Environmental Quality Objectives (EQO) approach can be followed to establish suitable effluent quality targets. The EQO method consists of the following steps; Evaluation of the local environmental characteristics. Identification of all potential contaminating components of all effluent streams. Identification of environmental characteristics sensitive to effluent discharge levels. Consideration of the potential end use of waters in the receiving environment e.g. drinking water supply, agricultural use.
0

Determining the distribution, fate and impact of all substances contained in the effluent steam. Impact should consider factors including toxicity, persistency, accumulation and biodegradability.

Taking all these factors into consideration allows the setting of realistic and environmentally responsible standards governing the level of contaminants in waste water discharges to ensure minimal environmental impact. In some instances, the EQO approach may lead to the adoption of standards that are more stringent than that required by local regulations. However, in other cases the EQO approach may be used as a logical and defensible basis to support the setting of realistic discharge levels for a particular environment. SlPM EP0/6 should be contacted for more information on the EQO approach.

4.3. 4.3.1.

WATER INJECTION General
For the purposes of this manual, the term water injection is used to mean the injection of waste water into the production reservoir for the purpose of assisting hydrocarbon recovery. However, in some cases, only the production water component of the waste waters is considered suitable for water injection, with the remaining waste waters disposed using alternative methods. The term disposal injection is used to define the injection of waste water into non-producing formations for the purposes of disposal only. This is discussed separately in section 4.4 The injection of water into a production reservoir to assist the recovery of oil reserves is a relatively well established procedure. Both surface waters (sea, river and lake water) and subsurface waters (aquifer and produced water) have been satisfactorily injected in a variety of locations. The following discussions briefly introduce the water treatment considerations that need to be addressed to ensure the satisfactory injection of water as a means of both hydrocarbon recovery and waste water disposal. The discussions are orientated to the injection of produced waters which are normally the largest waste water stream, however the general principles apply to most water sources. This information has been summarised from the SlPM Water Injection Manual (currently EP-63600, revised edition expected by 1st quarter of 1994). For more detailed information on water injection the SlPM Water Injection Manual (currently being updated) takes precedence over this manual.

4.3.2.

Water compatibility
Water injection of produced water is only possible if the water is determined to be compatible with the production reservoir. The investigation of water compatibility should address the following considerations:
0

Compatibility with the formation. Chemical incompatibility may result in the expansion of clay minerals or oxidation reactions due to the presence of oxygen (most injection water is maintained oxygen free). Physical incompatibility may result in the migration of fine solid particles through the formation (either carried by the injection water or dislodged from the formation) with the potential for blocking pores and consequent reduction in formation permeability. Compatibility with formation fluids. Incompatibility with formation fluids can result in changes in the chemical equilibrium of the formation fluids, potentially leading to scale formation in the
Noit

0

SlPM Droiling Mrriiivcl. EP 93-1315, Rrv I . I .

1993, Filr

twiie

= .IC//AP.DOC

Puge 4-3

4. Water disposal
reservoir, tubing or in surface production facilities.

Compatibility with other injection waters. In some cases, waste water will form only part of the total volume of required injection water. In this instance the compatibility of the waste water with the other injection waters (e.g. sea water) must be established, as well as the compatibility of the combined waters with the formation itself and the formation fluids.

4.3.3.

Permeability impairment
Treatment of water before injection is required to avoid potential impairment of the permeability of the formation. Table 4.4 lists potential means of permeability impairment and references the sections of the current SlPM Water Injection Manual (EP-63600) where additional information can be found. Of these potential means of permeability impairment, the removal of suspended solids and dispersed hydrocarbons from the produced water are of most importance to the selection of water treatment equipment.
Table 4.4 Potential sources of permeability impairment Impairment source Suspended solids Coalescing oil droplets Formationof insoluble scales Pre-engineering evaluation method Method of prevention

Ref

. . . . .
31,

Source water survey Evaluation of filtration specification Source water analysis Analysis of source water and formation water Computer aided scale prediction Dynamic tests of chemical inhibitors Core sample flooding tests Petro-graphicalanalysis Core sample flooding tests Petro-graphicalanalysis Source water analysis Source water analysis
EP-63600, August 1985

.
0

Fine filtration Fine filtration Fine filtration Emulsification Prevent commingling of incompatible fluids or use chemical inhibitors Sulphate removal membranes Modify water injection program Chemical injection Modify water injection program Chemical injection Inject chemical biocides Materials and coatings selection Chemical inhibitor injection Cathodic protection

L
3 . 2 . 1 3.2.1 3.2.3 3.3.3 3.2.2 4.4 4.3 4.3 3.2.5 7.2
6.0

. . .
I

Swelling of reservoir clays Movement of reservoir fines Bacteriologicalsolids Corrosion products
[ I ] Ref: SlPM Water Injection Mal

I

4.3.3.1.

Solids removal
Solids present in injected water have the potential to be trapped in the formation around the well bore, resulting in a flow restriction and a deterioration in injectivity. Such blockage will adversely affect the ability of the injection well to accept the requisite waste water volumes. Individual reservoirs differ in tolerance for both the quantity and the size distribution of the solids in the injection water. Factors that will affect the ability of the reservoir to tolerate solids include; The permeability and pore structure of the basic reservoir material. The degree of fracturing present in the reservoir. The physical properties of the hydrocarbons present in the reservoir. Core flooding tests can give some indication to the tolerance of the reservoir to the presence of solids. However field experience often contradicts the results of core flooding tests, either by injectivity impairment of “tolerant” reservoirs or in the unexpected tolerance of supposedly “tight” reservoirs. Typical quality requirements for water injection of sea water in the North Sea are 98% removal of solid particles larger than 2 pm with a particle number count of less than 25 parlicl,es per 0.05 ml of water. This corresponds to the typical water quality that can be achieved with conventional filtration equipment. A well-head guard filter can be used to achieve a further reduction in solids by the removal of up to 100% of particles larger than 0.6 pm.

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4. Water disposal
However, the setting of excessively strict water injection specifications is very expensive in terms of additional process equipment, particularly for offshore installations. Specifications should not be set as simply the best achievable quality, but should be justified by consideration of all relevant information. Issues such as down hole contamination of the water with corrosion/erosion products, the thermal fracturing of reservoirs and the costhenefit analysis of different treatment options should be considered.

4.3.3.2.

Hydrocarbon removal The presence of dispersed hydrocarbons in the injected water can also lead to permeability impairment. Dispersion of the hydrocarbon into the reservoir may result in the formation of a stable emulsion or sludge, often stabilised by the presence of solids. This emulsion may exhibit a very high viscosity and non-Newtonian rheological behaviour, resulting in plugging of the reservoir. In addition, dispersed oil may alter the wetting properties of the formation and may form an oil bank in the proximity of the well bore, also reducing permeability. For many water injection schemes the dispersed hydrocarbons are removed along with the suspended solids by filtration. In this case the hydrocarbon droplet size in the feed stream and the level of dissolved hydrocarbons present will determine the level of hydrocarbons remaining in the filtered water. Typical design levels are less than 5 mg/l of dispersed hydrocarbons.

4.3.4.

Secondary waste water streams
While water injection can be an efficient method for disposal of waste water, particularly produced water, consideration must also be given to the disposal of secondary waste water streams from the production facilities such as process water, drains water and ballast water. In some cases, it may be possible to mix secondary waste waters with the water for water injection. However the suitability of this must be carefully evaluated as it may potentially introduce more problems than it solves, due to the following considerations;
0

The possibility of scale formation from mixing incompatible waters The introduction of bacteria and/or oxygen into the injection water. The optimum rate of water injection for production purposes may not correspond with the rate required for disposal of secondary waste waters. During initial years of production there may be no requirement for any water injection. Flow rates of secondary water may be seasonally variable.

0

0

0

In most instances, waters for injection and secondary sources of water are riot mixed. In these circumstances, even though the bulk of the waste water may be disposed of through water injection, waste water treatment facilities must still be provided for the disposal of secondary waste water streams.

4.4. 4.4.1.

DISPOSAL INJECTION
General
Disposal injection differs from water injection in that the water stream is injected only for the purpose of disposal, not as a means of assisting production rates. Disposal injection injects waste water into subsurface formations other than the production reservoir, such as aquifers or exhausted production reservoirs.

As with water injection, the information provided in this Deoiling Manual is a summary only, concentrating on the aspects of disposal injection relevant to the selection and design of deoiling equipment. For more detailed information the user is referred to the SlPM Water Injection Manual (currently EP-63600, revised edition expected by 1st quarter of 1994).

4.4.2.

Water quality constraints

4.4.2.1. Disposal reservoir constraints
The drilling and completion of any well is expensive and the water for disposal should be treated to a quality sufficient to ensure that the capacity of the disposal formation is not restricted by avoidable damage. Therefore, until proven otherwise, the constraints imposed by the reservoir on disposal water are broadly similar to those outlined for water injection in section 4.3.
SlPM Deorltng
Mntrriiil.

EP 97-1315, Rev 1 I , Niiv 1993. File

iiitine

= 4ClIAP DOC

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4. Water disposal
However, there is typically more latitude allowed in the treatment of disposal water than allowed for injection water and there are numerous cases of the disposal injection of waste water with minimal treatment. A more relaxed water quality specification for disposal water is often acceptable on the basis of: The disposal formation may be specifically chosen on the basis of a high tolerance for poor quality disposal water. Stimulation of the disposal formation may be possible. In many cases, water for disposal injection may only need to be treated to level similar to typical offshore surface disposal specifications, i.e. below 40 mg/l dispersed hydrocarbons. This can be used as a starting point for design. However, considering the potential impact on equipment design, these limits should be confirmed through normal reservoir plugging evaluations as discussed in the SlPM Water Injection Manual.

4.4.2.2.

Environmental constraints Disposal injection of waste water should avoid subsurface structures that may be used or linked to sources of water for industrial, agricultural or domestic purposes.

4.4.2.3.

Regulatory constraints Countries which utilise aquifers as a source of water for industrial, agricultural or domestic purposes will often have regulations governing the disposal of waste waters in subsurface structures.

4.5.

SECONDARY (REJECT) STREAM DISPOSAL General
The main focus of most deoiling system designs is generally the quality of effluent water stream. However, the contaminants removed from a waste water stream are simply moved from the waste water stream to some secondary waste stream. The design of a water treatment facility must consider the potential disposal requirements of secondary waste streams that may be generated. Secondary waste streams may include concentrated hydrocarbon streams, sludge and waste gas streams. In particular, the techniques used for the removal of dissolved hydrocarbons often result in the generation of large secondary streams that must be treated, regenerated or disposed.

4.5.1.

4.5.2.
4.5.2.1.

Disposal options
Export with hydrocarbons Secondary waste streams may often be spiked into the product hydrocarbon stream and exported. This is often possible as the secondary waste stream may be relatively concentrated and small in volume compared to the overall product stream. This is a common method of "disposing" the hydrocarbons recovered from deoiling processes. However, it should be recognised that this method of disposal is simply transferring potential contaminants to downstream processing activities where the same contaminants may need to be removed a second time. In some cases it may be more economic to treat the waste upstream rather than transfer the problem downstream.

4.5.2.2.

Recycling to process Many process schemes recycle secondary waste streams to the start of the process. This is satisfactory provided at some point in the process there is a satisfactory purge of the contaminant from the process systern. Care must be taken to avoid the potential accumulation of contaminants in the process through recycling. For example, the recycling of sludge, such as from oil/water interfaces, should be avoided. Such sludges are relatively stable and are unlikely to break down without additional treatment. As a result they will tend to accumulate in the process. Solids may also accumulate in the process and may eventually reach a stage where they are responsible for the stabilisation of sludges or emulsions.

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4. Water disposal
4.5.2.3. Disposal to atmosphere Some deoiling processes will result in the generation of a waste gas stream, for example stripping of hydrocarbons from water using a gas. The resulting gas stream containing the stripped hydrocarbons is typically discharged to the flare system or fuel gas system, and may be subject to regulations governing discharges to atmosphere. 4.5.2.4.

Disposal for separate treatment
In some circumstances, secondary waste streams will be removed from the process for separate treatment. The two best examples are emulsion sludges and solid sludges. Solid sludges are discussed in more detail in section 4.5.3. Emulsion sludges are stable oil/water emulsions, oflen accumulating at the oiVwater interface. Such emulsions are oflen stabilised by the presence of emulsifying agents such as surfactants, waxes or fine solids. These emulsions are often withdrawn for separate treatment in dedicated sludge treatment plants. The handling and treatment of emulsion sludges is addressed in more detail in the current SlPM Dehydration/Deoiling manual (EP 89-0150, section 5.7, due to be updated by mid 1994). Some of the processes discussed for solid sludges in the following section can also be applied to emulsion sludges.

4.5.3.
4.5.3.1.

Sludges
General Sludges are secondary waste streams containing accumulated solids, organic material and biomass. Sludge is typically produced by biological waste treatment, but also includes accumulated solid wastes from other types of deoiling equipment and hydrocarbon and water emulsion sludges. The handling and treatment of emulsion sludges is addressed in more detail in the current SlPM Dehydration/Deoiling manual (EP 89-0150, section 5.7, due to be updated). However a number of the sludge treatment processes presented in the following discussions may also be applied to emulsion sludges. The potential significance of sludge streams should not be underestimated. They may contain concentrated levels of environmentally significant components such as hydrocarbons, heavy metals and radionuclides and may be subject to special environmental regulations. Adequate provision must be made for the removal, handling, storage and treatment of solid and sludge waste products at the design stage. Table 4.5 summarises the various treatment stages that can be applied to sludges. Depending on the application, a sludge treatment process may utilise all or only some of these stages. Each unit operation is briefly addressed in the following discussions. The "Sand Wash Design Manual'' EP 93-1270, due to be issued in the 4th quarter of 1993, contains additional information on the handling and treatment of accumulated solids.

4.5.3.2.

Stabilisation Stabilisation is the treatment stage designed to convert the sludge to a safe and stable state. This involves the breakdown of degradable organic material to discourage microbial growth (putrescibility control) and to reduce the levels of micro-organisms to minimise any threat of pathogens.
A number of biological and chemical processes can be used to stabilise the sludge. Stabilisation can also be used as a means of reducing the volume and weight of sludge.

4.5.3.3.

Conditioning Conditioning is designed to improve the dewatering characteristics of the sludge. Chemical conditioning includes the use of coagulation and flocculation chemicals to form larger, more readily separated agglomerations of solids. Elutriation is a washing stage that can be used before chemical conditioning to improve the effectiveness of the chemical treatment. Heat treatment can break down the structure of the sludge, resulting in a more easily dewatered sludge.

4.5.3.4.

Concentration Concentration of the sludge often precedes dewatering to reduce the volume of sludge to be dewatered.

SlPM Deoilinl: M(r111ra1. EP 93-1315. Rev 1.1. Nov 1993, File minw = 4CIIAP.DOC

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4. Water disposal
Concentration can be achieved by gravity thickening, dissolved air flotation or centrifuging, with gravity thickening being the most common method, The concentrated sludge underflow from a gravity thickener would typically contain in the order of 8 to 15% solids by volume.

4.5.3.5.Dewatering
Sludge dewatering removes sufficient water from the sludge to form a damp solid or sludge cake. A range of processes are available, including centrifuging, filtration, drying beds and drying lagoons. Centrifuges can typically achieve a dewatered sludge of 25 to 40% volume solids, while filtration can typically achieve 40 to 60% volume solids. A vibrating membrane has also been developed for dewatering sludges.

4.5.3.6.Drying
Drying of a sludge typically takes the form of heat treatment to produce a relatively dry sludge with a water content of only 8 to 10%. Incineration is a more extreme form of drying where the combustible elements of the sludge are converted to combustion products. Incineration will still leave some sludge residue in the form of ash which will still require a suitable form of disposal.

4.5.3.7.Residual disposal
Any sludge handling system must include a method for the disposal of final residues. The most common methods of disposal are sanitary land fill, application on agricultural land and deep well injection. Land farming of sludges can be particularly effective in tropical regions. Residual disposal will usually require suitable facilities for the handling, storage and transportation of the residue.
Table 4.5 Sludge treatment unit operations Unit operation Stabilisation Methods Aerobic or anaerobic digestion Chemical stabilisation Composting Heat treatment Irradiation Lagooning Chemical addition Elutriation Heat treatment Centrifuging Dissolved air flotation Gravity settling Centrifuging Drying beds Lagoons Filtration Chemical fixation Land application/farming Land fill Well injection Function Putrescibility control Pathogen destruction Odour control Volume and weight reduction Gashy product production Improve dewatering Improve solids capture Improve processing rate Thickening Water removal Blending of sludges Water removal Volume and weight reduction End product utilisation Disposalto waste End product utilisation
;orbitt, R.A., ISBN 0-07-013158-9,

Conditioning Concentration Dewatering

Residual disposal

Reference: Standard handbook of Environmental Engineering

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5. Waste water sampling
. .. ...... ... .......... .......... ... .... ... ......... .. ...

.....

5.1.

GENERAL
A waste water stream is a complex mixture of constituents, both dissolved in the water and present in the dispersed hydrocarbon phase. In addition to the liquid phases, gas and solid phases may also be present. In E & P operations, most routine samples of effluent water are taken for the determination of hydrocarbon content. For this analysis, the most important consideration is obtaining a representative sample of the dispersed hydrocarbons. A representative sample is required to ensure; Accurate measurement of the overall hydrocarbon content. An inaccurate measurement indicating a high hydrocarbon concentration may have implications in meeting regulatory effluent quality standards. Effective process design and operation. The accurate measurement of hydrocarbon concentration and droplet size distribution of the dispersed phase is critical for the correct selection, design and operation of deoiling equipment. Because of the potential complexity of a waste water effluent stream, and the regulatory significance of the results of waste water analysis, it is important that there is a clear understanding of the factors associated with sampling that may influence the results of subsequent analysis procedures. The importance of following good sampling practices cannot be understated. Laboratory analyses, operational decisions, process and equipment design and environmental protection are all activities of which sampling forms the first step. Poor sampling degrades the value of these subsequent activities. At the very least, poor sampling wastes time and effort as repeat samples are required to confirm uncertain results. The procedures discussed in this section are designed for the sampling of waste water streams. For the sampling of well stream fluids (oil, gas, condensate etc.) the user is referred to "Guidelines for manual sampling and analysis of hydrocarbon fluids", SIPM EP 92-0980. A number of references are made to ASTM standard methods (American Society for Testing and Materials). These standards are readily available through most technical library services or can be requested from SIPM.

5.2.

SAMPLE POINTS Location of sampling points
The following guidelines should be followed to ensure the correct location of a sample point.

5.2.1.

d d

Sample points should preferably be located in a region of turbulent flow. The transition to turbulent flow starts when the Reynolds number is greater than 3000. Sample points.should be at least 3 pipe diameters downstream and 1 pipe diameter upstream of any flow disturbance such as a bend, pump, manifold etc. (ASTM D 4177-82, Ref.l.07.1 .c). Sample points should preferably be located in vertical sections of piping where the fluid flow is upwards. The fluids in vertical piping are not subject to phase separation and stratification due to gravity. Sample points should be located both immediately upstream and downstream of the deoiling equipment with no potential shear sources (e.g. control valves) between the deoiling equipment and the sample point. Sample points should provide an effective and safe means for the collection and disposal of the fluid flow required to flush the sample point. Sample points should not be located on or immediately after bends or other flow disturbances. Forces exerted on the fluid by flow disturbances (particularly bends) will result in a separation of phases of different densities.

d
d d
%

SIPM Droiliitx Monitril, EP 93-1315, Rcv 1.1. Nov 1993. File ii(iiiir = SCIIAP.DOC

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5. Waste water sampling
%
Samples should not be taken from the surface of either a water stream or a body of water (e.g. sampling from the liquid surface in a vessel or tank). The surface layer will not be representative of the bulk of the fluid.

Effective operation and trouble-shooting of deoiling operations can only be performed with the provision of adequate sampling points both upstream and downstream of all stages of deoiling equipment. Designs for new facilities should always be reviewed for the provision of sufficient and suitably sited sampling points. In some cases, legislation may specify a particular sampling location for the monitoring of effluent water streams before discharge into the environment. Such a sample point may be required in addition to the sampling points required for the normal monitoring and control of deoiling equipment.

5.2.2.

Orientation of sampling points
The following guidelines should be followed to ensure the correct orientation of a sample point.

4 4
%

Sample points should always use a sample quill to ensure a representative sample. The sample quill should preferably extend to the centre of the pipe or at least a distance of D/3 away from the piping wall (Ref.l.07.1 .n).
If sampling from horizontal piping cannot be avoided, samples should not be taken from the top or bottom of piping. The sample quill should be installed either to allow sampling from the centre of the pipe or at a point along the line of the "nine o'clock'' or "three o'clock'' positions.

5.2.3.

Design of sampling quills
To date, most water samples taken in the field are from sample points mounted directly on the pipe wall. However this is a poor sample location as the velocity and turbulence of the fluid at the pipe wall is relatively low and surface and wall effects may bias the sample. In addition, sampling from the wall requires the flow profile to divert through 90" to enter the sample piping. Due to these changes in the flow profile, the concentration and size distribution of any dispersed solid, liquid or gas phase in the sample is unlikely to be representative of the bulk fluid. To ensure a more representative sample, sample points should be fitted with a quill extension. Figure 5.1 illustrates two suitable sampling quills designed to allow the sample to enter the quill with minimum disturbance. These designs are taken from the reference "On-line process stream analysis - Sample take-off and transportation, March 1992", DEP 32.31.50.1 O-Gen.

I

Figure 5.1 Sample quills from DEP 32.31.50.10-Gen

The first design has the end of the sampling quill bevelled at 45".This is a cheap and relatively simple design. The second design uses a curved end to smooth the flow path into the sample quill. Both designs have the advantage of being straight which allows the quill to be inserted in a slim fitting similar to a thermowell and allows the probe to be easily withdrawn as required for maintenance. The sample point design illustrated in Figure 5.2 has a long radius bend designed to minimise any
5-2
SlPM Droilinl: Miuiitctl. EP 93-1315. Rrv 1.1. Nov 1993, File nume = 5CHAP.DOC

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5. Waste water samtdinn
disturbance to the flow pattern at the tip of the quill. A larger fitting is required to allow the curved quill to be inserted. The quill is offset to ensure the tip of the quill is as far away as possible from any flow disturbances around the fitting.

Figure 5.2 Sample point design utilising a curved quill

HIJOZb16P

The following guidelines should be applied to all sample quills. The wall thickness of the quill should be as thin as possible and the tip of the quill should be bevelled to a sharp edge. With a blunt edged quill a damming effect can occur upstream of the tip, deflecting droplets away from the quill. As previously mentioned, the quill should preferably extend to the centre of the pipe or at least a distance of D/3 away from the piping wall. However the length of the quill may be restricted by the need to withstand the mechanical forces exerted by the flow in the pipe. A procedure for determining the maximum length of a sample quill is given in “Standard Practice for Automatic Sampling of Petroleum and Petroleum Products”, ASTM D 4177-82 (Ref.l.07.1 .c). Care must be taken to ensure that the quill is installed with the opening facing in the upstream direction. The sample quill should be fabricated with an integral labelled tab to ensure correct orientation. The internal diameter of the sample quill must be sized to allow an isokinetic fluid velocity through the quill while ensuring the volumetric flow rate is within the capacity of the sampling equipment. Section 5.5.2 discusses isokinetic sampling in more detail.

5.3.

SAMPLE CONTAINERS
Materials

5.3.1.

5.3.1.1, Glass
Glass sample containers are suitable for most water analyses. Glass sample bottles are preferred for non-routine samples, especially for the determination of heavy metals or when the sample will not be analysed immediately. The use of dark glass bottles will reduce photo-degradationof the sample. However, glass sample containers should not be used for samples from which small quantities of hardness, silica, sodium or potassium are to be determined.

5.3.1.2.

Plastics
High density linear polyethylene, polypropylene and Teflon containers are suitable for most water analysis duties. However users should be aware that these containers are slightly permeable to light volatile hydrocarbons and gases such as carbon dioxide. Mercury will also be lost from the sample through the walls of the sample container. Plastic containers are acceptable for routine determination of hydrocarbon content of water samples, as errors introduced by sampling considerations will far outweigh potential errors from sample container materials. However glass sample containers should preferably be used for non-routine analyses, heavy metal analyses, or when samples will not be analysed immediately.

SlPM Duriiling Mciriitcrl. EP 93-1315. Rev 1 . 1 .

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5. Waste water sampling
5.3.1.3. Sample container closures
In addition to the sample containers themselves, some consideration should also be given to the sample container lids and stoppers. These should also be made from glass or suitable inert plastics which will not absorb hydrocarbons from the sample. Aluminium foil lined closures should not be used when analysing for aluminium in samples that are strongly alkaline or acidic. Absorbent materials such as cork should not be used for lids or stoppers. Greases should not be used to assist the sealing of ground glass fittings.

5.3.2.

Cleaning of sample containers
All sample containers, new or used should be thoroughly cleaned before use. Sample bottles and lids should be scrupulously clean of all hydrocarbon residues. No traces of cleaning detergents should be left in the bottles as these may influence the coalescing and settling of the dispersed phase. The following typical glassware cleaning procedure has been extracted from ASTM D 3325-90, “Standard practice for preservation of water-borne oil samples” (Ref.l.07.2.a).

The cleaning steps consist of an initial wash with a warm aqueous detergent mixture followed by six hot tap water rinses, two rinses with reagent water, a rinse with reagent grade acetone and a final rinse with solvent such as pentane, hexane, cyclohexane, dichloromethane, or chloroform followed by drying in a clean oven at 105°C or hotter for 30 minutes. If the glassware requires cleaning under field conditions, it should be washed with warm aqueous detergent followed by extensive water rinsing. A solvent rinse with acetone should be made, if possible, followed by a lengthy air drying to remove residual solvent
More stringent cleaning procedures for both plastic and glass sample containers can be found in ASTM D 3694-92, “Standard Practice for Preparation of Sample Containers and for Preservation of Organic Constituents” (Ref.l.07.2.b). Sample containers for determination of trace substances such as heavy metals will require an even more thorough cleaning procedure. A typical procedure taken from the Thornton Research Centre (Ref.1.02.2.d) is as follows;

Sample containers are cleaned by standing overnight at room temperature containing 1:l hydrochloric acid. The containers are then rinsed clean with de-ionised water and allowed to stand overnight at room temperature containing 20% v/v nitric acid. The containers are finally thoroughly rinsed clean with de-ionised water, then stored in a particle and fume free environment prior to dispatch. Acids used should be analytical reagent grade.

5.4.

SELECTION OF SAMPLING METHOD
The selection of the correct method for sampling water containing a dispersed liquid phase can be simply summarised by the following decision tree;
Sampling to measure droplet size distribution?
I
I
I

I
I

I

I Droplet size distribution must not be altered by Simply ensure isokinetic conditions are followed
at the point the sample enters the sample quill. This ensures a representative sample enters the sample system.
Reference section 5.5 the sampling. lsokinetic conditions to be followed where the sample enters the sample quill with neutral behaviour in the remainder of the sample system. Reference section 5.6

Routine Sampling

Droplet Size Distribution Sampling

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5. Waste water sampling
Routine sampling does not consider the droplet size distribution of the dispersed phase, thus provided isokinetic conditions exist in the sample quill, the conditions in the remainder of the sampling system will not influence the subsequent analysis. Droplet size distribution sampling requires a more careful design of the sampling system to ensure that the droplet size distribution is not altered by the sampling. These requirements are covered in more detail in section 5.6.

It should be noted that for both routine sampling and sampling for the measurement of droplet size distribution, to ensure a representative sample enters the sample system;
0

A sample quill should be used. lsokinetic conditions should be maintained in the sample quill itself.

5.5.

ROUTINE SAMPLING
Introduction
The concentration of contaminants in effluent waters is often very low. The concentration of mineral hydrocarbons in effluent waters is generally lower than 40 parts hydrocarbon per million parts water (typical offshore effluent specification) while the concentration of other contaminants such as heavy metals is typically a thousand times lower, in the order of parts per billion. Due to these low concentrations, careful sampling practices are required to ensure samples of effluent water are representative and not contaminated.

5.5.1.

5.5.2.

lsokinetic conditions
lsokinetic sampling is simply achieved by ensuring that the velocity of the sample in the sampling quill is equal to the velocity of the fluid in the process line being sampled. This is critical when sampling streams containing a dispersed phase such as hydrocarbon droplets or suspended solids.

L
O

L

* =

0

-

0

0

-/------

- 0

Vsarnple

Visokinetic

Vsarnple = Visokinetic

Vsarnple

> Visokinetic

Figure 5.3 Effect of sampling under isokinetic and non isokinetic conditions

Figure 5.3 illustrates the influence of the sampling velocity at the tip of the sampling quill. When not sampling at the correct isokinetic velocity the disturbance in the flow profile can result in a bias in the sampled size distribution due to the different inertial properties of the various sized elements of the dispersed phase. lsokinetic sampling is only effective when a sampling quill is used. Sampling from a simple side mounted sample point will introduce large changes in the flow profile which will tend to bias the sample whether or not isokinetic conditions are followed. For consistency isokinetic conditions should be used when sampling from a side mounted sample point, however to ensure a representative sample a sample quill should be fitted.

To determine the isokinetic sampling rate, the velocity of the fluid in the main process line should be calculated. Then, knowing the internal diameter of the sample quill, the appropriate volumetric sampling flow rate can be calculated which will result in the same fluid velocity in the sample quill as in the process line. The sampling flow rate for a non-hazardous water stream would usually be simply measured by timing the filling of a known volume (bucket and stop-watch technique).
Table 5.1 gives an indication of the typical sampling rates required to achieve isokinetic sampling through different sized sample quills, based on an typical flow velocity of 2.5 m/s in the process line being sampled. Figures 5.5 and 5.6 at the end of this chapter can be used to quickly determine the
SlPM Deoilir~gMiiniral. EP 93-1 715, Rev I 1. Nov 1993. File m r i i i c = SCIIAP DOC

Puxc 5-5

5. Waste water sampling
correct sampling rates for other flow velocities.
Table 5.1 Typical sampling rates for isokinetic sampling

&diameter
(mm)

Sampling quill

I

Required sampling . flow rate (m3/h)

I

Time to fill a 10 litre bucket (seconds)

12.5 15.8 20.9 26.6

Basis: Assumes 2.5 m/sec fluid velocity in process line. Inside diameters correspondto schedule 40 pipe with 3/8",1/2", 3 4 " and 1' nominaloutside diameters .

I

1.11 1.76 3.10 5.02

32 20 12 7
I

5.5.3.

Procedure for routine sampling
The following procedures can be followed for most routine sampling of low pressure waste water streams. Section 5.6 discusses techniques for sampling from higher pressure lines and sampling to measure droplet size distributions. Care must be taken to ensure that the inside of the sample container or container closure is not contaminated once in the field. Contamination could result from thin hydrocarbon films deposited from the production environment or from hands or gloves. The sample point should be opened and allowed to run to flush the sampling line. The sampling system should be designed for the safe containment and disposal of this flushing flow. Once the sample point has been flushed the flow rate from the sample line should be adjusted to give the required isokinetic sampling flow rate. Once the flow has stabilised the sample may be taken. The sample should be taken without rinsing the sample container. Rinsing will result in a higher hydrocarbon content by leaving a film of hydrocarbons on the internal surfaces of the container. When filling, the sample bottle should not be allowed to overflow as this will result in the concentration of dispersed solids or hydrocarbons which remain in the sample container as the water overflows. Samples should be clearly labelled and any abnormal conditions such as process upsets, operational problems or difficulties in obtaining samples should be noted. If a sample is to be retaken the initial sample should be discarded and a new sample taken using a fresh sample bottle. Repeat samples should be taken to confirm unusual results. Unusual results which are not confirmed are often simply disregarded as "spurious" results which may conceal an actual operating problem. Samples containing dispersed hydrocarbons should not be subdivided as phase separation and coalescence of the hydrocarbons may result in an uneven division. When determining the hydrocarbon concentration the entire sample should be analysed and the size of the sample collected should take this into consideration.

5.6.

SAMPLING TO MEASURE DROPLET SIZE DISTRIBUTIONS Introduction
Sampling to measure droplet size distribution is more complicated than routine sampling as the size distribution of the dispersed droplets must not be altered by the sampling procedure. Two steps must generally be followed. The sampling conditions at the point that the sample enters the sample quill must be isokinetic to ensure that the dispersed material is representatively sampled.

5.6.1.

POKC 5-6

SIPM Deoilinp Momctrl. EP 93-1315. Rrv 1.1, Nirv 1993, File ncrmr = 5CHAP.DOC

5. Waste water sampling
The conditions after the sample quill must be neutral. This maintains the droplet size distribution without encouraging either further droplet shearing or coalescence.

5.6.2.

Sampling procedure to determine droplet size distribution
The first step in sampling to determine the droplet size distribution is maintaining isokinetic conditions in the sampling quill. As previously discussed in section 5.4.2, isokinetic sampling simply requires that the velocity of the sample through the sampling quill is the same as the velocity in the line being sampled. lsokinetic sampling should be used as the first stage of all sampling to ensure a representative sample enters the sampling system. Once a representative sample has entered the sample system, the objective is then to ensure the droplet size distribution is not altered. Thus after the isokinetic sample quill the sampling system should be designed to avoid both shearing and coalescing forces i.e. maintaining neutral conditions. Neutral sampling is not quite the same as isoenergetic sampling. lsoenergetic sampling is strictly defined as ensuring that the mixing energy exerted on the sample by the sampling system is approximately equal to the mixing energy that would be exerted on the fluid in the process line being sampled. In practice, what is actually required is that the sampling system does not alter the droplet size distribution of the sample once it has left the process line. Thus if a sample is taken from a coalescing zone, further coalescence in the sample system is not desired, just as further shear is not required when sampling from a high shear area. The user is required to exercise some judgement in designing a sampling system such neutral conditions are maintained and droplet size distribution is not altered, avoiding both droplet shear or coalescence. Appendix B contains an example illustrating a calculation procedure that may be used to estimate the correct sampling rate for any sampling configuration.

5.6.3.
5.6.3.1.

Effect of process pressure on sampling and droplet size distributions
Discharging to atmospheric pressure The majority of water samples are taken through a sample line and an isolation valve with the sample discharged to atmospheric pressure. Due to the inherent pressure drop through the sampling system this method of sampling is unlikely to be neutral and it is probable that the droplet size distribution of the dispersed phase will be altered by the sampling. Thus unless the pressure drop is low and special precautions are taken to prevent droplet shearing, droplet size distributions should not be measured when discharging a sample to atmospheric pressure.

5.6.3.2.

Pressurised sampling Where the droplet size distribution is to be measured, sampling should be conducted using a pressurised sampling method. Figure 5.4 illustrates one such sampling technique using a flow-through sample bottle. The sample quill should be sized to achieve isokinetic conditions at the point where the sample enters the sample system, however the remainder of the sample piping should be sized to achieve neutral conditions. Isolation valves should be full bore valves to minimise shear and the flow rate through the sample bottle should be regulated by using the downstream needle valve.

w Needle valve

H Full bore isolationvalves
3 1 Ouick releasecoupling

Figure 5.4 Flow-through sample bottle

~~

SlPM Droilinx Moiiicol. EP 93-1315, Rrv I I . Nov 1993, Fik

iiiiiiie

= SCIIAP DOC

PuRe 5-7

5. Waste water sampling
The sample stream should be allowed to flow through the sample bottle until at least twice the volume of the sample bottle has been passed. Care should be taken to ensure that upstream valves are fully open to minimise pressure drop. Once the sample bottle has been flushed through, the downstream isolation valve should be closed, followed by the upstream isolation valve. The sample bottle can then be disconnected from the sample line and with the sample bottle orientated vertically the sample can be carefully depressurised using the upper valve. The depressurised sample can then be drained from the bottle and the size distribution of the sample measured. This sampling procedure ensures that the sample is not sheared across a valve during depressurisation. The orientation of the sample bottle should consider the relative density of the fluids. For example, if the dispersed phase is heavier than water (e.g. solids or some heavy oils), when the sample fluid velocity slows as it enters the sample bottle these dense particles or droplets may be able to settle against the upwards flow and accumulate in the sample bottle. In this case the sample bottle may need to be orientated downwards. Where visual inspection of the sample during sampling is required, a transparent sample container with a working pressure and temperature of 50 barg and 60°C respectively can be ordered from KSEPL (reference 1.07.1 .f). An alternative system which does not require flushing is a sample bottle fitted with a floating piston. Prior to sampling the piston is forced against one end of the sampler by charging with a liquid or inert gas. The sample bottle is then fitted to the sample point and the sample admitted to the sample bottle by withdrawing the charging liquid or gas at the desired rate. This sampling device is discussed in more detail in Appendix 2 of “Guidelines for manual sampling and analysis of hydrocarbon fluids”, EP 92-0980, (Ref 1.07.1 .m).

5.6.3.3.

Depressurisation Both the atmospheric and pressurised sampling methods discussed above eventually depressure the sample. This depressurisation is required by some analytical equipment for the measure of the droplet size distribution. However, depressurisation may lead to the generation of gas bubbles which may have a number of detrimental effects such as; Interference with the method used to measure the droplet size distribution e.g. by obscuration or optical interference. Gas bubbles may be registered as dispersed droplets. Gas bubbles generated within a dispersed droplet may shear the droplet as they evolve, altering the droplet size distribution.

If gas evolution may be a problem, droplet size distributions should be measured at process conditions without depressurisation using either the KSLA microphotograph technique or the GalaiNortoil particle/droplet size analyser (see chapter 6).

5.7.
5.7.1.

SAMPLE PRESERVATION AND STORAGE

Introduction
After sampling, a sample will tend to ”age” through the action of chemical and biological reactions. This ageing will tend to alter the composition and character of the sample and thus should be prevented or minimised. Samples should preferably be analysed or utilised immediately to minimise the effect of ageing. However when this is not possible, appropriate storage and preservation techniques should be used to extend the representative life of the sample. Brief summaries on sample preservation and storage are given in the following discussions. Additional information can be obtained from the following references,
0

“Standard Practice for the Preservation of Waterborne Oil Samples”, ASTM (Ref.l.07.2.a).

D

3325-90

0

“Standard Practice for Preparation of Sample Containers and for Preservation of Organic Constituents”, ASTM D 3694-92 (Ref.1.07.2.b). “Standard Practice for Estimation of Holding Time for Water Samples Containing Organic
SIPM Denilinp Mii/iwi/,EP 9.1-1315, Rev I . I , NOV1993. File nomr = 5CliAP.DOC

0

Puae

5-8

5. Waste water sampling
Constituents”, ASTM D 451 5-85 (Ref.l.07.2.c).

5.7.2.

Chemical Preservation
The life of a sample can be extended by the addition of preservative chemicals to the sample. These chemicals inhibit the chemical and biological changes that may alter the composition of the sample over time. The most common preservation technique used is the acidification of samples which are to be analysed for hydrocarbon content. Acidification (typically using hydrochloric acid) to a pH <: 2 will inhibit the biological degradation of organic materials. Different preservation chemicals may be required for the preservation of other components of the sample. In some cases separate samples using different preservation chemicals may be required.

5.7.3.

Sample storage
To maximise the storage life the sample should be stored in dark glass bottles in a dark area to minimise photo-degradation of the sample. Storage at a temperature of approximately 5°C will inhibit biological and chemical reactions. Freezing should be avoided, especially for emulsions where the inter-facial film may be destroyed by the formation of ice crystals. Air, or more specifically oxygen, should be excluded from the sample to prevent oxidation reactions. Air may be displaced from sample containers using a relatively inert gas such as nitrogen.
. )

.

5. Waste water sampling

6.0 5.0 4.0

ID=26.6mm

1
ID=20.9mm

0

E

B

_. 0)

-0

.2 2.0

E. a
3

3 . 0

-

a

P

1.0 -

ID=12.5mm

0.0

9

60.0

E: ln
0)

50.0

c

n
1 -

_ .

5 30.0
c

2
m

3

40.0

; F

g! .3

'0

P

20.0

i =

E

0-

g!

10.0

0.0 0.00

0.50

1.oo

1.50

2.00

2.50

3.00

3.50

4.00

Fluid velocity in main process line (mlsec)

Figure 5.6 Time required to fill a 10 litre container while sampling under isokinetic conditions through different sample quill inside diameters (Inside diameters correspond to schedule 40 pipe with 3/8", 1/2", 3/4" and 1" nominal outside diameters)

P U ~5CIO

SIPM Droilinx Mitnuitl, EP 93-1315, Rev 1.1. Niiv 1993. File nome = 5CHAP.DOC

6. Waste water analysis

6.1.

GENERAL
For most E & P deoiling operations, two of the most important characteristics of the water stream are the concentration of the dispersed and dissolved hydrocarbons and the size distribution of the dispersed hydrocarbon phase. Infrared absorption analysis is the most common procedure for determining the concentration of hydrocarbons in waste water and the advantages and limitations of this method of analysis are presented in this chapter. Of particular importance is the recognition of the following potential limitations in many infrared analysis procedures; The absorption frequencies used may not be sensitive to the presence of aromatic hydrocarbons. The standard procedures do not differentiate between dispersed and dissolved hydrocarbons. The accuracy of the measurement is dependent on the use of suitable calibration samples. Infrared adsorption analysis is discussed in detail in section 6.2. However other methods of analysis are also available and these are briefly discussed in section 6.3. On-line oil-in-water monitors are discussed in section 6.4. The size distribution of the dispersed hydrocarbon phase is one of the most important parameters governing the performance of most deoiling equipment. The measurement of droplet size distributions is discussed in section 6.5.

6.2.
6.2.1.

HYDROCARBONS INFRARED ABSORPTION ANALYSIS

-

Introduction
The most common method of measuring the concentration of hydrocarbons in water is infrared absorption. This method is based on the absorption of infrared light by the carbon-hydrogen (C-H) bonds present in hydrocarbons. The procedure generally consists of the following steps. Sample preservation and preparation. Extraction of the hydrocarbons from the water using an organic solvent. Conditioning of the extract to remove solids, water and polar hydrocarbons. Measurement of the infrared absorption at one or a number of infrared light wavelengths. Standard infrared analysis procedures measure the total quantity of hydrocarbons extracted from the water by the solvent and make no distinction between dispersed and dissolved hydrocarbons. Table C.l and C.2 in Appendix C summarise the key characteristics of 15 published procedures for the determination of hydrocarbons in water. It should be noted that the results obtained from infrared analysis are not an absolute measure of the hydrocarbon content of effluent waters, but are calibrated against reference standards. Inappropriate calibration standards will result in an inaccurate determination of hydrocarbon content. In particular, the aromatic content of effluent samples may be excluded from the analysis due to inappropriate calibration standards or the use of infrared wavelengths which are not absorbed by the carbon-hydrogen bonds present in aromatics. In addition, many infrared analysis procedures do not measure polar hydrocarbons which are removed from the sample before analysis. This includes both polar hydrocarbons derived from the well-stream (organic acids and phenols) and polar process chemicals such as methanol and glycols. It should be noted that infrared hydrocarbon analysis is only a relative determination of hydrocarbon content in water. When a more complete breakdown of the hydrocarbons present in the effluent waters is required a more absolute method of analysis such as gas chromatography must be used.

6. Waste water analysis
6.2.2.
Sample preparation

6.2.2.1.

Acidification
If the sample is not to be analysed immediately, it is common practice to acidify the sample. Acidification has the following beneficial effects;
Minimises hydrocarbon losses due to biological degradation. Improves phase separation by countering the presence of alkaline based emulsion stabilisers. Dissolves any precipitated calcium carbonate. Hydrochloric acid is typically used to avoid potential precipitation problems that may occur with anions from other acids (e.g. sulphates from sulphuric acid). ASTM D 3694-92, “Standard Practice for Preparation of Sample Containers and for Preservation of Organic Constituents“ (Ref.l.07.2.b), recommends acidification to a pH i2 to inhibit biological activity for biodegradable organic chemicals. Acidification has a potential problem in that it may change the dissociation equilibrium of weak organic acids. These liberated organic acids would then be detected by the subsequent hydrocarbon analysis and incorrectly reported as part of the hydrocarbon component of the water. This problem can be avoided by ensuring that after the organics are extracted from the water phase, the extract is passed through a suitable polar absorbent. As the liberated organic acids are polar, they will be removed by the absorbent and will not be measured as part of the mineral hydrocarbon content of the water.

6.2.2.2.

Gas purging
The Paris Commission (Parcom) guidelines governing water discharges from offshore platforms in the North Sea allows samples to be purged with a nitrogen gas flow (at approximately 1 litrehin) for a period of 45 seconds at a temperature of 30°C. The justification for this gas purging is to remove light components that would normally flash into the gas phase on discharge into the environment, leaving only the hydrocarbons that will remain in the aqueous environment. However gas purging will also strip volatile hydrocarbons from the sample. Up to 75% of the BTEX aromatics may be stripped by this purge, resulting in an underestimate of the hydrocarbon content of the effluent stream.

6.2.3.

Hydrocarbon extraction

6.2.3.1.

Selection of solvent
After sample preparation the hydrocarbon content of the water is extracted using a solvent. Carbon tetrachloride (CCI,) and Freon 113 are the two most commonly used solvents, however both are being phased out of use. Carbon tetrachloride requires careful use to ensure occupational health safety. Freon 113 is one of the CFC chemicals recognised as harmful to the ozone layer and under the Montreal Protocol must be eventually phased out of use. A number of alternative solvents could potentially replace the currently used solvents, though none of the alternatives has been officially accepted for infrared analysis. The following reference discusses the use and performance of range of alternative solvents.
“A protocol for determining oil and grease in produced waters”, Simms, K., Zaidi, A., Bhargave, O., 1992 International produced water symposium, San Diego, Feb 4-7 1992. Reprinted in Produced Water, edited by J.P. Ray and F.R. Engelhart, Plenum Press, NY, 1992. Available from SlPM on request (Ref.l.02.1 .a).

An alternative is the elimination of solvent altogether. Manufacturers are developing infrared absorption, ultraviolet absorption and ultraviolet fluorescence techniques that can be applied directly to the water sample without the use of a solvent. KSEPL are also in the process of developing a direct infrared absorption method. The primary aim of these developments is application as on-line oil-in-water monitors and commercial units are currently available. However when tested, the performance of these units has typically not been satisfactory and at this stage these methods cannot be considered as suitable replacements for the current solvent extraction based methods.

PlI,qc! 6-2

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6. Waste water analysis
6.2.3.2. Extraction Extraction of the hydrocarbons from the waste water is achieved by adding the solvent to the waste water sample and ensuring intimate mixing of the phases. There is quite a wide variation in extraction procedures between the methods presented in Appendix C. Key differences are; The use of mechanical mixing or manual mixing. Mechanical mixing is preferred to ensure a repeatable result. The German DIN, Dutch NEN and Swedish standards utilise a centrifuging step after mixing to ensure complete separation of the water and organic phases. The extraction procedure does not differentiate between dissolved and dispersed hydrocarbons present in the water sample. Both will be extracted from the water sample and measured in the subsequent infrared analysis. As dispersed hydrocarbons in the sample will tend to coalesce over time, it is difficult to accurately subdivide a waste water sample. Thus the extraction must be performed on the entire water sample. The extraction may be performed either in the sample container itself or else the sample container and the sample container lid or stopper should be thoroughly rinsed with the solvent to ensure all residual hydrocarbons are extracted. 6.2.3.3. Filtration and drying To remove solids and water droplets that may be present it is normal practice to filter the solvent extract. All final traces of water may be removed by passing the extract though an anhydrous drying column containing sodium sulphate or other suitable water adsorbent.

6.2.4.

Removal of polar compounds
Polar hydrocarbons, including compounds such as organic acids and phenols, are normally present in the waste water streams from oil and gas production. Their polar nature makes them relatively soluble in water and they may have a relatively high concentration in effluent water streams. The solvent extraction procedure extracts both mineral hydrocarbons and a proportion of the polar hydrocarbons from the water sample. Regulations governing hydrocarbon levels in effluent streams generally exclude (or are interpreted to exclude) polar and dissolved hydrocarbons. Thus the polar hydrocarbons are often removed from the solvent extract before measuring the hydrocarbon content. Polar hydrocarbons are removed by passing the extract though a column containing a polar absorbent such as Florisil (activated silica-gel) or alumina (A1203). However, it should be noted that this absorbent may also remove some mineral hydrocarbons with polar characteristics from the sample, such as high molecular weight aromatic compounds.

6.2.5.
6.2.5.1.

Infrared analysis
Basis of measurement Infrared analysis is based on the absorption of infrared light by the C-H bonds present in hydrocarbons, with the absorption being related to the concentration of hydrocarbons. The solvent extract obtained from the previous procedures is scanned over a range of infrared light wavelengths in an infrared spectrophotometer. The absorption at characteristic wavelengths is related to the presence of particular C-H bonds as illustrated in Table 6.1. The presence of any of these groups will result in some absorption, hence the need to remove polar hydrocarbons before the absorption is measured. Similarly, the solvent used for the hydrocarbon extraction must be selected on the basis of not contributing to the infrared absorption, hence the use of halogenated solvents. Many infrared analysis procedures only measure absorption for the CH, group (see Table C2 in Appendix C). This is generally satisfactory as this is the most common carbon-hydrogen group present in mineral oils. However, aromatic hydrocarbons consist largely of CH bonds. If the absorption is not measured at the wavelength absorbed by these bonds (3.30 pm), these compounds will not contribute to the absorption and may go undetected (though this also depends on other factors such as the composition of the calibration sample). This could lead to a underestimate of the hydrocarbon content in effluent waters,

6. Waste water analysis
particularly when measuring the hydrocarbon discharges from gas production operations where the dissolved aromatic content of the effluent may be quite high.
Table 6.1 Infrared wavelengths absorbed by hydrocarbon groups Group Wavelength

(11171)
CH CH3

m-5
3030 2959 2924 2857

Characteristic

3.30 3.38 3.42 3.50

Low molecular weight aromatics Saturated hydrocarbons Long straight chain saturated hydrocarbons and cycloalkanes Long straight chain saturated hydrocarbons and cycloalkanes

> CH2 > CH,

6.2.5.2.

Calibration Once the absorption of the extract has been measured it must be converted into the required analytical measurement. This is achieved by comparison with the absorption measured for a known oil or reference oil calibration sample. Known oils Known oils are calibration samples made by mixing water with known quantities of a hydrocarbon sample taken from another part of the process. A typical source for the known oil may be the hydrocarbon reject stream of a water treatment package. Such known oils may not be completely representative of the hydrocarbons present in the effluent sample, especially if the water treatment system has additional separation stages after the point where the known hydrocarbon is obtained. The known oil may also be subject to a degree of "weathering" which may alter its absorption. However, in general, known oils are likely to be more representative of the actual hydrocarbons in the sample than the alternative calibration methods. Reference oils Reference oils are calibration samples made by mixing known quantities of a defined mixture of hydrocarbons. As an example, the reference oil defined by the Netherlands NEN 6675 standard consists of 37.5% iso-octane, 37.5% cetane and 25.0% benzene. The inherent drawback in the use of a reference oil is that if the composition of the hydrocarbons in the effluent stream is significantly different to that of the reference oil the accuracy of the hydrocarbon measurement will be reduced. The absolute accuracy of the method will also be reduced if the hydrocarbons in the sample contain a significant fraction of fully substituted carbon atoms i.e. carbon atoms with no C-H bonds. These fully substituted carbons atoms will not contribute to the absorption and thus will not be accounted for unless the reference oil used also contains a similar proportion of fully substituted carbon atoms. The advantage of reference oils is that they may be specified as part of standard method, allowing the same reference mixture to be used consistently in different locations. This at least provides a consistent basis for comparison of results from different locations and allows for the checking of procedures by independent authorities. However the accuracy of the result will be lower due to the variation between the actual hydrocarbons in each sample and the hydrocarbons in the reference oil. Soecific absorDtion coefficients An alternative to using calibration samples is the use of specific absorption coefficients. These coefficients can be built into equations which relate the measured absorption directly to the hydrocarbon content. As with use of a reference oil, the disadvantage of this process is that it assumes the composition of the

PU,qC

6-4

SIPM Droilirip Mor~rtcrl.EP 93-1315. K r v 1.1. N o v 199.7, F i l ~ ri(tnie = 6CHAP.DOC

6. Waste water analvsis
effluent stream is similar to that of the sample used to calculate the specific absorption coefficients. Again, carbon atoms that are fully substituted with non-hydrogen bonds will not be measured and will be excluded from the measured hydrocarbon content, This can be overcome by the use of correction factors, however such factors must be empirically determined for each application.

6.2.5.3. Results
Units of measurement The concentration of hydrocarbons present in water should generally be expressed using the unit of mg/l. The basis for the ppm unit (parts per million) is often poorly (or not) defined and could be interpreted as either a volume or mass basis. In some cases, legislation may require the reporting of results in alternate units such as mg/kg, ppm(w) or ppm(v). Accuracv

It can be seen from the discussions above that the accuracy of measuring the concentration of hydrocarbons in water will be dependent on a number of factors:
Obtaining a representative sample. The effectiveness of the extraction stage. This is in turn governed by factors such as the solubility of the hydrocarbons in the chosen solvent, the method and period of agitation used during extraction, then number of extraction stages and the effective separation of the solvent from the water phase. The potential loss of hydrocarbons during the removal of polar hydrocarbons from the extract. The measurement of the absorption at suitable wavelengths. The suitability of the calibration method. The accuracy of the method is generally reported to be in the order of +looh.

6.3. 6.3.1.

HYDROCARBONS OTHER METHODS Dispersed and dissolved hydrocarbons
Most deoiling equipment installed at E 8 P sites is only capable of removing dispersed hydrocarbons. Being able to differentiate between dispersed and dissolved hydrocarbons may be necessary to evaluate the performance of deoiling equipment. The most common methods used for the determination of hydrocarbon levels in waste waters involve the extraction of the hydrocarbons from the water phase using a solvent. Both dispersed and dissolved hydrocarbons will be extracted by the solvent and the total hydrocarbon content of the sample will be determined, not just the dispersed hydrocarbons. The simplest method to differentiate between dissolved and dispersed hydrocarbons is to perform the infrared analysis procedure on two effluent samples. The first effluent sample is analysed normally, thus measuring the total hydrocarbon content. The second effluent sample is filtered through a suitably fine filter to remove the dispersed hydrocarbons. The filtrate will then only contain the dissolved hydrocarbons which can be measured using the normal analysis procedure. The dispersed hydrocarbon content can then be calculated by subtracting the dissolved hydrocarbon content from the total hydrocarbon content.

-

6.3.2.

Gravimetric analysis
A solvent is used to extract the hydrocarbon content from the effluent sample. The extract is filtered to remove solids, water and salt, then evaporated under standard conditions to leave a residue. The residue is weighed and is reported as the hydrocarbon content. Gravimetric analysis tends to underestimate the concentration of hydrocarbons in water due to the loss of lighter hydrocarbons during the evaporation procedure. Comparative trials indicate that the gravimetric method may measure a hydrocarbon concentration in the order of 20% lower than infrared analysis (Ref.l.02.1 .a). This agrees with a 20% variation measured at a Shell crude oil terminal (Ref.2.05.2.e).

6. Waste water analysis
However, gravimetric analysis has the advantage in that apart from evaporation losses it is an absolute analysis and is independent of calibration errors.

6.3.3.

Visible spectrum colourimetry
A solvent is used to extract the hydrocarbon content from the effluent sample. The extract is then measured for absorption in the visible light spectrum or is visually compared with fresh reference samples of hydrocarbons in solvent. This method has the advantage that dissolved gases and many other non-oily organic compounds, being colourless, do not interfere with the measurement. Other advantages are; Solvents containing carbon-hydrogen bonds can be used.

It is not normally necessary to filter, dry or pass the sample through an absorption column.
The method is simple, cheap and portable and suitable for use under difficult conditions. However, the method may have a tendency to underestimate hydrocarbon content as the coloured components in crude oil are very easily absorbed onto surfaces and may be lost.

6.3.4.

Gas chromatography
The hydrocarbon content of the effluent sample is extracted with a suitable solvent and injected into a gas chromatography column which separates hydrocarbons in order of boiling point. Gas chromatography gives a detailed analysis of the composition and may be applied for special studies, but is generally too time consuming for routine use. are not detected The main disadvantage of this method is that high boiling point components (>300"C) as they are not carried through the column. The sensitivity of the method is O.lmg/l for oil, for single components less than 0.01 mg/l.

6.3.5.

Others
A range of other methods can be used for determination of hydrocarbon content, particularly in trying to measure hydrocarbon content on-line without solvent extraction. Infrared light scattering and ultraviolet absorption methods have been used for on-line instruments which are discussed in more detail in section 6.4 and Appendix D.

6.3.5.1.

Ultraviolet absorption Aromatics and other compounds with conjugated or pseudo-conjugated double bonds will absorb UV light. If the typical concentration of these particular hydrocarbons is known, the UV absorption can be related to the overall hydrocarbon content. Dual wavelength UV beams are sometimes used, the first measuring the absorption of the aromatics and the second acting as a reference to compensate for fouling and turbidity.

6.3.5.2.

Ultraviolet fluorescence spectrometry Aromatics and other compounds with conjugated or pseudo-conjugated doubfe bonds will also fluoresce when exposed to suitable ultraviolet light. The fluorescence can be related to the hydrocarbon content of the effluent sample.

6.3.5.3.

Concentration derived from droplet size analysis Dispersed oil-in-water takes the form of discrete oil droplets suspended in the continuous water phase. If the number and size of the hydrocarbon droplets is known, the volume of hydrocarbon in the water sample can be determined by calculating the cumulative volume of the hydrocarbon droplets. Knowing the average density of the dispersed hydrocarbons present allows the total hydrocarbon concentration to be calculated. Ultrasonic oil-in-water monitors operate on the basis of recognising the presence of dispersed droplets. An ultrasonic signal is reflected back by dispersed hydrocarbons in the sample to give an indication of the hydrocarbon content. The result will be affected by the droplet size, therefore the sample must be homogenised before analysis. Droplet size analysers are available which allow continuous on-line measurement of droplet size

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6. Waste water analysis
distributions. However, the disadvantage of this method is that it will only measure the concentration of dispersed hydrocarbons, dissolved hydrocarbons will not be measured. There is also potential for interference from gas bubbles and solid particles and the technique will become more inaccurate if a significant quantity of the hydrocarbons are present as very small droplets (e5pm). More information on particle size analysers can be found in section 6.5.

6.4.
6.4.1.

ON-LINE OIL-IN-WATER ANALYSERS

General
The development of an on-line oil-in-water monitor has been pursued by a number of manufacturers. Continuous measurement of the hydrocarbon content in the effluent waters from production sites would have the following potential benefits. More rapid detection of excess hydrocarbon content in effluent discharges. More feedback on the operation of deoiling equipment, promoting improvements in operational procedures and equipment design. Minimisation of manual sampling and analysis requirements. A range of commercial oil-in-water monitors have been tested by KSEPL and in trials at the Orkney Water Test Centre (OWTC). Although some of the meters tested have shown potential, at the time of testing none could be recommended as suitable for continuous operation in an operating environment. However, it should be recognised that the suitability of continuous oil-in-water monitors is often gauged on their absolute accuracy and their potential to replace current sampling and analysis procedures. Although commercial monitors may not yet be suitable for this purpose, their use in less rigorous applications should not be overlooked. Commercially available monitors could potentially be used in the following applications: To give a continuous indication of relative deoiling performance, calibrated by continued routine sampling and analysis. To act as an alarm, indicating when significant excursions occur in effluent hydrocarbon levels. This would facilitate more rapid corrective action, minimising the potential impact on downstream processes or the discharge environment.
A third series of oil-in-water monitor trials is to be conducted at the OWTC in the second half of 1993.

Table 6.2 lists the range of oil-in-water monitors that have been recently tested. The relevant reports are referenced in the Bibliography and the results from the OWTC trials have been summarised in Appendix D. Full copies of the reports are available from SlPM EPD/421 on request.
Table 6.2 Recently tested oil-in-water monitors Oil-in-water monitor tested Bristol Babcock OCD-30 Facet Mark Vlll Bilge Alarm Horiba OCMA-25 Monitek Micro-Pure MPS-D Pure Alert Oili-S Type 300 Schlumberger Oilcon EJB5l Teledyne 661R Fluoritest-S OCD-37 Oili-S Mark 1000 C Turner Model 10 Baird Petrolarm Horiba Ocma 25 Tested by OWTC - Phase I OWTC Phase I OWTC Phase I OWTC - Phase I OWTC - Phase I OWTC - Phase I & Phase II Report date March 90 March 90 March 90 March 90 & October 91 March 90 March 90 & October 91 March 90 October 91 October 91 Aug 90 8 October 91 October 91

-

OWTC - Phase I & Phase II

OWTC - Phase II

OWTC - Phase II OWTC Phase II KSEPL KSEPL

KSEPL & OWTC Phase II

-

-

Nov 88
May 84

6. Waste water analysis
6.5.
6.5.1.
MEASUREMENT OF PARTICLE AND DROPLET SIZES General
One of the most important criteria governing the selection and performance of deoiling equipment is the droplet size distribution of the dispersed hydrocarbons in the feed stream. As a result, the ability to accurately measure the droplet size distribution is a vital tool in the correct design and operation of deoiling equipment. This is particularly important when upgrading existing equipment, where the existing droplet size distribution can be measured and the optimum deoiling equipment can be selected.

6.5.2.

Sampling
The droplet size distribution of a dispersed hydrocarbon in water is constantly changing as a result of the emulsification and coalescing forces acting on the fluid. To accurately measure the droplet size distribution a careful sampling procedure must be followed. Sampling must be conducted to ensure; That the sample is representative. Obtaining a representative sample of a two phase liquid can be very difficult and a number of samples may be required with the results averaged. The sample point is correctly designed with a quill extension into the main fluid flow away from the piping wall. In some cases samples may be required at different points to ensure that the droplet distribution does not alter over the cross-section of the area being sampled (e.g. stratified flow). That iso-kinetic sampling is used at the point where the sample enters the sample system. This ensures the sample is not biased by changes in the flow profile. That iso-energetic conditions are maintained after the sample has entered the sample system. This will ensure that sampling does not alter the droplet size distribution by changing the dynamic equilibrium between coalescence and emulsification. Depressurisation of the sample should be avoided. Depressurisation is likely to alter the droplet size distribution through the imposition of shear forces on the sample and may lead to problems due to the evolution of gas bubbles. Appropriate procedures for sampling to determine droplet size distribution are discussed in detail in section 5.6.

6.5.3.

Potential problems in measuring droplet size distributions
In addition to the sampling considerations given above, the following points should also be considered when measuring droplet size distributions. Most equipment for the measurement of droplet size distribution operates at atmospheric pressure, making it impossible to avoid depressurisation of the sample. As already noted, depressurisation of the sample may have a significant effect on the droplet size distribution. Section 5.6.3 discusses the sampling of pressurised streams. Some equipment for the measurement of droplet size distribution may be temperature sensitive, requiring the sample to be cooled before measurement. This cooling may also affect the droplet size distribution. Coalescence may rapidly alter the size distribution of dispersed droplets. Samples must be analysed as quickly as possible. Solid particles and gas bubbles present in the sample may be detected as droplets, leading to a skewed size distribution.

6.5.4.

Droplet size distribution analysers
A number of different methods are currently available for the measurement of droplet size distribution.

6.5.4.1. Aperture counting (Electricalzone sensing)
Aperture counting based droplet size analysers were developed by Coulter Inc. The dispersed
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6. Waste water analysis
hydrocarbon droplets pass though a small, electrically charged aperture. The passage of the droplet results in a disturbance in the electrical field. From the number and magnitude of the electrical disturbances the size distribution of the droplets can be determined. The correct size of the aperture is linked to the size distribution being measured. If the aperture is too small, deformation of the droplet may occur as it passes through the aperture. In some cases the sample must be diluted with an isotonic liquid to achieve a suitable droplet population density, however this dilution may influence the droplet size distribution. The aperture counting method requires the continuous phase to be electrically conductive and may not be suitable for water-in-oil emulsions.

6.5.4.2. Diffraction based methods
Diffraction based methods infer the droplet size distribution from the diffraction patterns caused by the interference between suspended hydrocarbon droplets and a laser beam. Such instruments can typically measure particle sizes down to the order of O.1pm. Diffraction based methods are sensitive to the number of droplets in the sample. Too few droplets may not give a statistically significant result while too many droplets may result in optical interference with the measurement. Not all equipment warns the user that these errors may be occurring.

6.5.4.3. Time of transition
Time of transition based methods measure the interaction pulses generated as droplets intersect a scanning laser beam. Analysis of the interaction pulses determines the droplet size distribution. The interaction pulses are affected by the shape of the particle allowing differentiation between particles of different shape. Thus solid particles such as sand or corrosion products, which tend to have asymmetrical shapes can be differentiated from symmetrical hydrocarbon droplets. As with diffraction based methods, the number of droplets in the sample may influence the result. Too few droplets may not give a statistically significant result while too many droplets may result in optical interference with the measurement. Not all equipment warns the user that these errors may be occurring.

6.5.4.4. Imaging Methods
KS14,
KSLA have developed an image analysis method for measuring droplet size distribution. An isokinetically sampled side stream is diverted from the main process line and is directed through a cuvette. The stream is then isolated at process pressures (up to 300 barg) and temperatures and the hydrocarbon droplets are allowed a short time to rise to the sight glass of the cuvette. A photograph of the settled droplets is then taken through a microscope. As the droplets must be visible in the photograph this method is only practical when the continuous phase is relatively transparent. The resulting photographs are digitised and processed through image analysis algorithms to determine the size distribution of the hydrocarbon droplets. Sufficient samples and photographs must be analysed to ensure that the size distribution is representative. Statistical analysis can be used to identify the number of samples required to achieve a statistically significant result. This technique has the advantage that the photographs are taken at process temperatures and pressures, thus minimising possible distortions of the droplet size distribution due to depressurising the sample to atmospheric pressure. The method requires a trained operator and the resulting photographs must be sent to KSLA for image analysis. As a result this method of measuring droplet size distribution is restricted to specific investigations and not routine analysis. More information on the KSLA method of measuring droplet size distribution can be obtained from the following reference: "Droplet size distribution analysis with an image-analysis system, OiVwater separation (1989-1990)", Molenaar, H.J., Fens, T.W., Bonnie, J.H.M., KSLA report number AMGR.90.108, SlPM report number EP-no. 90-2982, (Ref.l.04.1 .c).

6. Waste water analysis

Others
Visual imaging of the dispersed hydrocarbon droplets is also available as an option with the VortoiEalai particle size analysers. A visual image of the dispersed droplets or solids is obtained using a CCD video camera microscope. The resulting image is not directly used for determining size distribution, however the image is be analysed for shape based criteria such as area, shape factor and aspect ratios and can be used to give a visual impression of the droplets and particles being measured. This method has the advantage in that the image is obtained from a flowing sample, not requiring the sample to be isolated or requiring the droplets to settle. The sample cell is rated for pressures up to 40 barg allowing for the size analysis of many streams at process temperatures and pressures. Other alternative image analysis services similar to the KSLA method are offered by independent companies. Examples include Quantimet, Joyce-Loebl, SCIL, TIM etc. Additional details can be obtained from KSLA, EE/4.

6.5.5. 6.5.5.1.

Particle size analyser trials

OWTC trials
A selection of particle size analysers were tested at the Orkney Water Test Centre over the period of November 1990 to February 1991. The following report was issued and is available from SIPM EPD/421 on request. “Particle size analyser trials conducted at the Orkney Water Test Centre November 1990 - February 1991”, Tullock, S.J., Oct 1992, EP-No.92-1952 The name, basis of operation and sample condition of the particle size monitors tested is listed in Table 6.3. A more detailed summary of the results from the trial is included in Appendix E.
Table 6.3 Particle size analysers tested at OWTC Particle size analyser Coulter LS130 Coulter Multisizer Vortoil/Galai CIS1002 Lasentec Partec 250 Malvern Mastersizer Basis of operation Laser diffraction Aperture counting Laser time of transition Forward scattering Laser time of transition Backward scattering Laser diffraction Sample Condition
-~

Batch, sample depressurised Batch, sample depressuhed, sample dilution may be required. Continuous, at process conditions up to 40 barg. Continuous, analysis probe can be directly inserted in process piping up to 10 barg. Batch or continuous, sample depressurised

6.5.5.2.

KSLA trials of the VortoiVGalai
The OWTC indicated that the Vortoil/Galai size analyser showed considerable promise, especially as it is capable of operating at higher temperatures and pressures than conventional size analysis equipment. Additional trials have been conducted by KSLA to compare the performance of the VortoiVGalai design with the KSLA image analysis method. Results of these trials are summarised in Appendix E.

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7. Equipment Selection and System Integration

7.1.

INTRODUCTION
In many installations, the majority of design or operating effort is concentrated on the hydrocarbon producing systems with only relatively brief consideration given to the waste water treatment system. In particular, water treatment facilities are often regarded as "end of pipe" solutions to a water treatment "problem".

A preferable situation is where water treatment is considered as an integral part of the total process design. Integration of water treatment equipment into the overall process system will result in a more efficient and cost effective facility.
Dehydration and deoiling processes should be considered as a single system with the emphasis on complementary design. Examples where such integration has brought improvements in operation include;
0

Minimisation of shear and promotion of coalescence in flow lines, pipe lines and piping systems upstream of dehydration has improved the quality of both oil and water outlet streams. The use of plate packs in primary separators to improve the quality of both oil and water outlet streams.
A gaskondensate installation with hydrocyclones operating at a high separator pressure (circa 120 barg) to minimise droplet shearing. A gashondensate installation designed to avoid the use of corrosion inhibitors (which stabilise small hydrocarbon droplets) and with the gashquid separator designed for effective three phase separation at high pressure.

The use of continuous dehydration designs in preference to batch dehydration has resulted in more consistent and stable feed streams to downstream water treatment equipment and more efficient water deoiling. These examples highlight the potential benefits that may be achieved by adopting a system approach to the design of the overall production facilities, particularly the dehydration and deoiling processes. This philosophy is examined in more detail in the following discussions. Section 7.2 presents guidelines to assist the user in effective process design and equipment selection for water treatment systems, while section 7.3 discusses overall system optimisation and integration considerations.

7.2. 7.2.1.

EQUIPMENT SELECTION AND SYSTEM DESIGN Introduction
Figure 7.1 on the following page presents a simple flow diagram illustrating the typical steps that should be followed when selecting a water treatment system. Each of the steps is addressed in more detail in the discussions in sections 7.2.2 to 7.2.1 0.

7.2.2.

Sources and magnitude of water streams (1)
The source of the waste water will strongly influence its characteristics. For example, water streams from oil production, gas production or ballast water systems would often require different water treatment facilities due to differing water characteristics. Clearly identifying the sources and magnitudes of the waste water streams will assist in the development of more efficient water treatment facilities. For example, small, difficult to treat streams may be handled separately rather than mixing the problem into the entire water stream. Section 2.2 discusses the sources of waste water and their typical characteristics.

7. Equipment Selection and System Integration
1.

IDENTIFY THE SOURCES AND MAGNITUDE

4.

SELECT A SUITABLE PROCESS LOCATION FOR THE WATER TREATMENT SYSTEM

NTiFY UPSTREAM PR COULD COMPLICATE THE WATER TREATMENT AND WHAT STEPS CAN BE TAKEN TO MAKE THE WATER EASIER TO TREAT

OR DISPOSAL OF SECONDARY STREAMS

Figure 7.1 Flow diagram for water treatment system design

7.2.3.

Identify contaminants in the waste water stream (2)
The full range of contaminants that may be present in the waste water stream should be identified. In addition to dispersed hydrocarbons, particular emphasis should be given to the presence of suspended solids, dissolved hydrocarbons and treatment chemicals. The majority of deoiling equipment used in E & P operations will only remove dispersed hydrocarbons. The presence of dissolved hydrocarbons may require more sophisticated equipment to meet the quality requirements in the treated water. The distinction between dispersed and dissolved hydrocarbons is particularly important for gas operations where dissolved hydrocarbons may constitute a significant proportion of the hydrocarbon content in the waste water.

A range of potential contaminants of waste waters is discussed in section 2.3.
7.2.4. Identify treated water quality requirements (3)

A suitable disposal route for the treated water should be identified. Both surface and subsurface disposal
options should be considered. Health, Safety and Environmental considerations should take first priority in the setting of treated water quality requirements. This also applies to sub-surface disposal as it is possible for water disposed into some subsurface structures to migrate to the surface environment through aquifers.

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7. Equipment Selection and System Integration
An Environmental Quality Objective approach may be used to evaluate the potential environmental impact of water discharges for both surface and subsurface disposal methods. Once HSE requirements have been satisfied, technical and regulatory requirements should be considered. Probable changes in environmental legislation over the design life of the installation should be identified and their potential impact on the design examined. The final target water quality will be the most stringent of the HSE, technical and legislative requirements. The setting of water quality targets is discussed in more detail in chapter 4.

7.2.5.

Select a suitable process location for the water treatment system (4)
Most water treatment equipment is located at the end of the process, often operating at or close to atmospheric pressure. However, whenever possible, consideration should be given to locating deoiling equipment further upstream in the process. Many types of deoiling equipment may be operated at elevated pressures (e.9. hydrocyclones, plate pack interceptors, flotation, filters etc.) This minimises the pressure drop between the water source and the water treatment equipment, thus minimising shear forces and maximising hydrocarbon droplet sizes. If possible, shear inducing devices such as control valves should be located downstream of water treatment facilities. Waste water streams are typically combined from a number of sources, however in many cases the flow from just one source may provide the bulk of the water. Consideration should be given to separate treatment at the source of the bulk waste water stream. An excellent example is a conventional three stage oil separation train. The bulk of the water is often separated in the first stage separator at a relatively high pressure, yet all this water is usually let down to a low pressure in order that the relatively small water streams from subsequent separators can report to a common low pressure water treatment system. A more effective installation may be to operate water treatment system immediately downstream of the first separator at an elevated pressure. The bulk of the water would then be effectively treated without being sheared through level control valves. The relatively low flows of water from other sources could be pumped to the water treatment system using low shear pumps or treated in separate facilities. Similarly, it may be found that the majority of contamination may come from just one source. Treating the contaminated stream separately may be more efficient than mixing the streams then having to remove the same contaminants from a larger stream. Consideration should also be given to the process conditions that will affect the separation mechanism. As discussed in Appendix F, the separation of two phases following Stokes Law will be sensitive to a number of variables which are affected by process conditions. In particular, the density differential and viscosity will be functions of the process temperature and the selection of the process location should consider the potential effect on the phase separation of the operating temperature.

7.2.6.

Identify upstream methods of improving ease of water treatment (5)
The performance of the water treatment system will be largely dependent on the nature of the feed to the system. The quality of the feed stream may often be improved by improving the performance of upstream processes, preferably through optimising the overall process design as illustrated in the introduction (7.1). The processes upstream of the water treatment system should be reviewed to determine whether there is scope to improve the water quality feeding the water treatment system. Improvements in water quality could encompass increases in dispersed droplet size, a reduction in hydrocarbon concentration, elimination of suspended solids or gases or the use of corrosion resistant materials to avoid the use of corrosion inhibitors. Improvements could be implemented by means such as minimising pressure drop through the system, fitting plate packs or coalescing devices to upstream vessels and improving process control. The optimisation of upstream processes is also addressed in section 7.3, System Optimisation and Integration.

7.2.7.

Select the number of treatment stages (6)
In theory, the hydrocarbon removal efficiency of some deoiling equipment may appear sufficient to achieve the required water treatment in a single stage. However, due to the variations in flow and
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7. Equipment Selection and System Integration
concentration that occur as part of normal operations it is unlikely that equipment will be able to operate at peak efficiency under all these conditions.

As a result, it is common practice to split the deoiling process into a number of stages. Operating with stages in series allows good results to be achieved with lower unit efficiencies, for example two deoiling stages in series operating at a relaxed 80% efficiency will have the same overall performance as a single stage operating at a 96% efficiency.
Operating with two or more stages also allows the upstream stages to optimise the feed conditions for the downstream stages, removing surges in flow rates or concentrations. The actual number of stages required will be determined by the ratio between the concentration of hydrocarbons or contaminants in the feed stream, and the quality requirements imposed on the effluent stream. In most cases at least two treatment stages will be required. Water treatment equipment can be broadly divided into the four stages illustrated in Table 7.1
Table 7.1 Typical water treatment stages and associated equipment Primary Treatment Skim tanks API separators Plate pack interceptors Shell standard CPI plate pack Coarse coalescers Secondary Treatment Induced gas flotation Dissolvedgas flotation Static hydrocyclones Rotary hydrocyclones Centrifuges Fine coalescers Polishing Treatment Crushed nut shell filters Dual media filters Cartridge filters Pre-coat filtration Membranes Tertiary Treatment Gas stripping Steam stripping Biological treatment Activated carbon absorption Solvent extraction Primary treatment is usually designed for the removal of large hydrocarbon droplets, large solid-particlesand hydrocarbon slugs. The primary stage will often be designed to absorb flow surges to provide a stable feed to subsequent water treatment stages.

Secondary treatment encompasses the bulk of deoiling equipment used in E & P operations. Secondary treatment is usually sufficient to reduce the dispersed hydrocarbon content below typical offshore discharge levels of 40 mgh (provided the droplet size and other water characteristics are within the operating envelope of the equipment).

Polishing stages are used for the further removal of dispersed hydrocarbons to levels typically below 10 mgh. Various filters are the most common methods used for polishing stage treatment. Polishing stages are often required where water is to be re-injected,for disposal from inshore or onshore based installations, or where feed is to pass to a tertiary treatment stage. Tertiary treatment encompasses techniques required to produce an effluent stream of high quality. Typical requirementsare a total hydrocarbon content of less than 5 r n g ,with strict restrictions on other variables such as BOD, heavy metals etc. Tertiary treatment encompasses a range of processes, with stripping techniques and biological methods most commonly used.

7.2.8.

Select the suitable deoiling equipment (7)
The most important variable influencing the selection of most water treatment equipment for the removal of dispersed hydrocarbon droplets is the hydrocarbon droplet size. The hydrocarbon removal efficiency of gravity based separation equipment is largely dependent on droplet size, most equipment having a minimum droplet size that can be efficiently separated. Figure 7.2 illustrates the typical minimum droplet sizes that can be separated by a range of equipment. The selection and design of any water treatment equipment should be based on a consideration of the probable droplet size that will be present in the water at the point of treatment. Unfortunately, at the design stage for a new installation, it is very difficult to predict the likely droplet size that may be present in the feed to the water treatment equipment. Appendix A provides some guidance on the factors that may influence droplet size. Comparisons may also be made to the performance of water treatment equipment or the measured droplet size distributions at existing installations with similar process and operating conditions.

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7. Equipment Selection and System Integration
The design of water treatment equipment to be added to existing installations should be based on field measurements of the hydrocarbon droplet size distribution. Such measurements give added confidence to a particular design and should allow the selection of the most cost effective treatment scheme.

I

Hydrocyclones

4
I

1

I

I

I

Centrifuges
Filtration
I I

I

10

100

Particle or droplet size (pm)

lo00

1

Figure 7.2 Typical minimum droplet sizes for deoiling equipment

It is apparent from Figure 7.2 that a number of water treatment equipment designs can be used to separate a given droplet size distribution. Once the droplet size criteria has been satisfied the selection of the water treatment system is governed by factors such as; Size and weight (particularly offshore) Capital cost Operating cost Ease of operation Maintenance requirements Flexibility of operation Generation of secondary waste streams

As a guide, Table 7.2 presents some guidance for the selection of different water treatment equipment designs. However, it must be stressed that for effective equipment selection all the steps presented in Figure 7.1 , particularly water and droplet size characterisation, should be followed.
For further guidance on the selection of deoiling equipment, the user is referred to the equipment summary tables presented in section 8.1 and the detailed discussions covering each equipment design presented in chapters 8 and 9.

7.2.9.

Treatment or disposal of secondary streams (8)
All water treatment systems will generate secondary streams such as concentrated hydrocarbon streams, sludges and stripping streams. Appropriate treatment or disposal methods for secondary streams must be clearly identified at the design stage with full consideration given to potential Health, Safety and Environmental implications. This is particularly important for tertiary treatment systems which may involve the removal of volatile organic compounds such as benzene from water. For more information reference should be made to section 4.5.

7.2.1 0.

System optimisation and integration (9)
Once the location and basic elements of the water treatment system have been defined, the design should be reviewed to identify scope for optimising the performance of the system and to ensure the design has been effectively integrated into the overall production process scheme. System optimisation and integration are discussed in more detail in section 7.3.

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Table 7.2 Selection criteria for water treatment systems Primarv Treatment Plate pack interceptors-Efficient primary treatment equipment. Can be designed to provide for degassing and solids removal and can be fitted into a wide range of equipment configurations. Can be used for most non-foulingapplications. Shell standard CPI plate pack Skimtanks API separators Coarse coalewers

A Shell standard plate pack design for onshore, atmospheric pressure applications. Good choice for drain waters, ballast waters etc.
Relatively inefficient. Typically selected on secondary considerations such as providing surge capacity or if conditions do not allow a plate pack design. For most applications superseded by the Shell CPI design. May be used upstream to enhance the performance of skim tanks.

Secondary Treatment Static hydrocyclones

Becoming preferred method of deoiling, especially offshore. Potential drawbacks are relatively high capital costs compared to flotation and less flexible performmce compared to rotary hydrocyclonesor centrifuges. Lower capex than alternativesand properly configured can give excellent performance. However, has higher weight and space, higher opex (chemical injection) and may require more operator attention.

Induced gas flotation

Dissolvedgas flotation Same comments as for induced gas flotation. Rotary hydrocyclones Falls between hydrocyclonesand centrifuges on price and performance. Should be considered if more flexibility or better performance than static hydrocyclone is required, but at a lower cost than a centrifuge. Should be considered for low flow, difficult separations such as water from gadcondensate operations. Excellent separation performance for dispersed hydrocarbons and solids, but expensive. Often only choice for difficult separations. Should be considered for low flow, difficult separations such as water from gas/condensate operations. Can be used upstream to enhance the performance of secondary equipment.

Centrifuges

Fine coalescers

Polishing T r e a t m e n t

Crushed nut shell filters Recommendedfor the filtration of produced water with dispersed hydrocarbon concentrations up to the order of 150 mg/l. Dual media filters Can be used for produced water with a low dispersed hydrocarbonconcentration, preferably less than 50 m u . Used where solidhydrocarbon loading is very low, for example as guard filters downstream of media type filters. Good performanceif solids and oil content are low (e5 m g ) , however generally not recommendeddue to problems with handling and disposing of pre-coat. Show promise but require further development for most deoiling applications. Could be considered for low flows of relatively clean (non fouling) waste waters.

Cartridge filters Pre-coat filtration Membranes

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7. Equipment Selection and System Integration
Table 7.2 (Continued) Selection criteria for water treatment systems

Tertiary Treatment
Air stripping

Commonly used onshore, relatively cheap. However requires suitable path for disposal of contaminated stripping gas. Presence of oxygen may cause problems Typically uses nitrogen or lean hydrocarbongas. Eliminates oxygen related problems, but oflen more expensive than air stripping. Nitrogen stripping requires source of nitrogen. Lean hydrocarbongas stripping may need compression to recover hydrocarbon gases. More expensive than gas stripping, however has the advantage in that the waste gas stream is relatively easily treated by condensation. Commonly used onshore to treat water to a standard required for disposal into inland waters e.g. rivers, lakes. Mainly used for the removal of dissolved organic contaminants. Salinity and variability of productionwaters may impose limitations. May be used for removal of low levels of specific contaminants such as heavy metals and hydrocarbons. However, regeneration or disposal of spend carbon must be addressed. May be effective if suitable solvent is readily available and there is a suitable solvent disposal or treatment route. KSLA compact design under development.

Gas stripping

Steam stripping Biological treatment

Activated carbon absorption Solvent extraction

7 . 3 . 7 . 3 . 1 .

SYSTEM OPTlMlSATlON AND INTEGRATION CONSIDERATIONS Introduction
To optimise the design or operation of water treatment equipment it should be considered as part of an overall production process, not as isolated, "end of pipe" equipment.
During the design or for the operation of water treatment systems, each of the topics addressed in the following discussions should be considered to ensure the performance of the water treatment system has been optimised and that the water treatment system is effectively integrated into the overall process scheme.

7 . 3 . 2 .

Maximising droplet size
As the performance of most deoiling equipment is strongly influenced by the size of the dispersed hydrocarbon droplet, every effort should be made to maximise the droplet size.
In particular, shear forces which generate small droplets should be minimised or avoided. Where possible, control valves should be located downstream of water treatment equipment. Feed pumps should be selected on the basis of having low shear characteristics. Piping routings and fittings upstream of water treatment systems should be designed to avoid introducing unnecessary shear forces or if possible located downstream of the water treatment system. Coalescence of dispersed hydrocarbon droplets should be promoted wherever possible.

7 . 3 . 3 .

Minimising the hydrocarbon content in the feed stream
The majority of deoiling equipment cannot achieve a fixed hydrocarbon concentration in the treated water, independent of the feed hydrocarbon concentration. The performance of most deoiling equipment is measured in terms of a hydrocarbon removal efficiency, which is a ratio between the hydrocarbon content in the feed and the outlet streams. Thus, even for equipment with very high hydrocarbon removal efficiencies, a high hydrocarbon content in the feed stream will result in a high hydrocarbon concentration in the outlet stream. The impact of this behaviour on system integration considerations is that it is often more effective to concentrate effort on minimising the hydrocarbon content in the feed to the deoiling system, rather than striving for marginal increases in the performance of the deoiling equipment itself. As previously discussed, using several stages of deoiling in series will often allow a better overall hydrocarbon removal efficiency to be achieved, especially in the face of peak hydrocarbon concentrations.

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7.3.4. Production separators
The main function of most production separators is the separation of gas from liquids and water from hydrocarbons. While the minimisation of the water remaining in the hydrocarbon stream must be the primary concern, consideration should also be given to the minimisation of the hydrocarbons remaining in the water. Where process conditions are suitable, the use of plate packs or coalescing devices in the production separators should be considered to reduce the quantity of hydrocarbons remaining in the water stream.

7.3.5.

Stable feed streams
Process equipment operates most efficiently when supplied with a constant, stable feed stream. However many water treatment systems are located at the end of the process and are subject to wide variations in process conditions from upstream operations. Where possible the flow to water treatment equipment should be smoothed by appropriate buffer capacity on feed streams or through improved control of upstream operations. As well as smoothing flow variations, the provision of buffer capacity allows for the averaging of peaks in hydrocarbon concentrations and can be used to promote additional coalescence of dispersed hydrocarbon droplets. An example is the water stream from continuous or batch dehydration. Water from batch dehydration is often difficult to treat as the flow rate will vary with the falling head in the dehydration tank, while the hydrocarbon concentration will increase as the oil interface is approached, on some occasions passing slugs of hydrocarbons to the downstream equipment. In contrast, continuous dehydration can result in a water stream which is stable in both flow rate and concentration, leading to improved deoiling performance.

7.3.6.

Recycle streams
The effect of recycle streams on process integration should be carefully considered. Recycle streams may often be contaminated with solids, chemicals or bacteria and recycling these streams may result in accumulation in the process. In particular, sludges or tight emulsions which accumulate at hydrocarbon/water interfaces should not be recycled to the process without appropriate treatment to break down the inherent stability of the sludge or emulsion. Where possible, reject streams from any equipment should be disposed by injecting into the hydrocarbon export stream provided sufficient dilution exists to avoid exceeding export quality specifications. This avoids the use of recycle streams. Alternatively, recycle streams may be processed in dedicated sludge or emulsion treating facilities. Treatment requirements for reject streams should be considered as part of the overall water treatment system. For example, conventional dual media filtration systems require additional equipment for the treatment of dirty back wash water.

7.3.7.

Mixing of water streams
Most hydrocarbon facilities will produce a number of waste water streams from different sources. Mixing of these streams for treatment in common water treatment facilities may lead to problems such as; Fluctuating feed rates and contaminant concentrations due to water arriving from several sources. This may lead to unstable operating conditions in water treatment equipment which will be detrimental to its performance. Waters from different sources may react to form undesirable compounds or precipitates. Introducing oxygenated waters may result in corrosion problems and the precipitation of oxides from the water. To avoid these potential problems, wherever possible consideration should be given to segregation of treatment facilities.

7.3.8.

Treatment chemicals
A wide range of treatment chemicals are commonly used to assist the production process such as demulsifiers, deoilers, antifoams, corrosion inhibitors and hydrate inhibitors.

Whenever a process chemical is used, its potential impact on the entire process system should be
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93-1315, Rev 1.1. Nov 1993, File nciine = ?Ci!AP.DOC

7. Equipment Selection and System Integration
considered. This should include the effect on downstream equipment, interaction with other treatment or residual chemicals and possible influence on upstream systems through recycle streams. Examples where the use of treatment chemicals can affect the overall process system include; Demulsifiers used to improve the dewatering of water-in-oil emulsions can result in the stabilisation of hydrocarbons droplets in the water phase Surface active chemicals such as corrosion inhibitors stabilising oil-in-water emulsions. In addition to potential operating problems, the use of chemicals incurs a range of additional costs such as the purchase cost of the chemical itself, the cost of transportation, storage and handling of the chemical and the operating and maintenance cost of chemical injection facilities. Finally, in many cases, treatment chemicals represent an additional contaminant may need to be subsequently removed to allow the safe discharge of waste streams into the environment. Due to these potential drawbacks, it is recommended that wherever possible, process systems should be designed to operate without the use of treatment chemicals and efforts be made to reduce the use of treatment chemicals wherever possible.

7.4.

EXAMPLES OF WATER TREATMENT SCHEMES
For examples of typical water treatment schemes reference should be made to section 8.5 of the SlPM Dehydration/Deoiling Manual EP 89-0150. Section 8.5 presents dehydration and deoiling process schemes from a selection of operating and conceptual process designs.

7.5.

WATER CHARACTERISATION CONSULTANCY SERVICES
There are a number of companies which can provide on-site water characterisation services. Such services may be used to determine the characteristics of a water stream from existing facilities before the design or upgrading of water treatment facilities. The scope of such services should be governed by specifications defining the requirements of the water characterisation such as sampling procedures, sample preservation and analysis methods. If required, SlPM can supply a typical work scope and specification which has been used for previous water characterisation programs. The basic work scope can then be modified to suit local requirements. SlPM EPD/42 can be contacted for the basic water characterisation work scope/specification and the names of companies who can provide on-site water characterisation services.

7.6.

PILOT PLANT TRIALS
Due to the wide variation of water characteristics, pilot plant trials of water treatment equipment are recommended wherever possible. This is particularly important where the performance of the water treatment equipment may be very dependent on the water chemistry, such as flotation processes. Trial units are available for most of the water treatment equipment discussed in this manual.

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7. Equipment Selection and System Integration

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8.1 Dispersed hydrocarbons - Introduction

8.1. 8.1 .l.

INTRODUCTION
Scope of chapter
Chapter 8 presents discussions on a range of proven deoiling equipment for the removal of dispersed hydrocarbons from water. Where applicable each discussion includes information on equipment design principles, performance characteristics and sizing guidelines. For the removal of dissolved hydrocarbons from water the user is referred to Chapter 9, while Chapter 10 presents new and as yet unproven technologies which may be used for the removal of dissolved and/or dispersed hydrocarbons from water. When considering any design or operational deoiling problem it is strongly recommended that the user reviews the system design information presented in Chapter 7. Improvements in deoiling equipment design or operation can often be made by consideration of the deoiling system within the context of the overall process. This is particularly true with respect to the influence of upstream shear characteristics on the droplet size distribution of the dispersed hydrocarbons reaching the deoiling process. Effective integration of the water treatment system into the overall system design'will result in the most efficient and cost effective solution.

8.1.2.

Equipment for dispersed hydrocarbons Summary tables
Following section 8.2 (Definitions), each equipment class is presented in an individual section containing relevant tables and figures for that equipment. Where suitable information is available, each section includes a summary table summarising the performance of the equipment in a range of tests, trials or operating installations. Table 8.1.1 presented on the following pages summarises the general performance characteristics of all the deoiling equipment covered in Chapter 8.

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Hydrocarbon removal efficiencies and outlet 111 concentrations 111 Coarse Upstream of other Coarse coalescer Higher hydrocarbon Dependanton inlet coalescers separation equipment. designs do not affect concentrationspromote droplet size. Refer to May be designed as droplets smaller than coalescence. No upper individualcases given e.g. combined coalescers 40 pm. limit on hydrocarbon in the summary serpentine concentration. tables in relevant paths. coarse and separators. section 01 Chapter 8. packlng Fine coalescers Typically cartridge type designs. Media bed COaleSCer8 Upstream of other separation equipment. May be designedas combined filters, coalescersand separators. Upstream of other Separation equipment. Usually designed as combined coalescers and separators. Cartridge designs can Higher hydrocatton coalesce droplets concentrations promote down to at least 10 coalescence. however pm. may result in greater louling.

Equipment

Location

Minimum droplet size separaIed

Recommended hydrocsrbon inlet concentrations

Solids handling

chemicals

Use of

Advantages

Disadvantages

Some (but not all) coarse Not normally coalescers can be used. designed to handle solids wilhout blockage.

Examples include SP packs, structured packing etc. Should improve the separation pertormance of downstream equipment. Coarse design resists blockage by fouling and solids, but limits coalescingpower lor small droplets. Excellent coalescing ability for small droplets. Particularly useful for condensate/water applications where droplet sizes are small but water flow rate is relatively low.

Coarse COaleSCerS Will Only improve performanceof downstream coarse separation equipment such as senling tanks. No significant coalescing effect lor small hydrocarbon droplets.

Dependant on inlet Cartridge designs will droplet size. Refer to block with solids. thus individualcases given solids in the feed should in the summary be minimised. May tables in relevant require cheap guard filter section of Chapter 8. upstream. Similar to a media High hydrocarbon Typically in the order Excessive solids will filter can coalesce concentrationswill of 15 m y l in the block media bed more droplets down to the assist coalescence but outlet stream. rapidly. Usually cleaned may result in more rapid by backwashing. order of 2 10 5 pm. fouling. High hydrocarbon Not applicable. concentrationscan be tolerated as not actually separating hydrocarbons. Rates of chemical addition may need to be adjustedto suit. No restriction Dependant on inlet droplet size. Reler to individualcases given in the summary tables in relevant section of Chapter 8.

Not normally used.

performance Fine cartndge bul COal may eSCerS be too have large good and expensive for large water flow rates. Cartridgeswill be fouled by some oils and by solids.

Coagulation Upstream of Droplets down to the Flocculation separation equipment. order of 2 to 5 pm Often used before can be coagulated. filtration or dissolved air flotation.

Designs often use oleophitic media or chemicals to make the media oteophilic. Dependson application Use coagulants to promote and chemistry of coagulation/flocculation. coalescence and Some solids may be poly-electrolytes bound into flocs and to promote removed. Others may Ilocculation. simply settle out. Solids will settle in tank Not normally or vessel, allowance can used. be made for accumulation and removal by jelling or manual cieaninq.

Gwd coalescence performance. Usually Media can be fouled by Some achieves coalescence and separation in a hydrocarbons. Equipment is relatively single vessel. Also removes solids. large and heavy.

Will increase the apparent droplet size. Requireschemicals. Downstream improving downstreamseparation. May be separation must be gentle to avoid destroyingflocs. able to flocculate solids to aid their removal by flotation or sedimentation.

Skim tanks and vessels

Primary separation, often used as surge vessels.

150 pm

Provide surge capacity, remove slugs of Large weight and space requirements. hydrocatbans, Homogenisestreams from Short circuiting likely in larger tanks and vessels. Under typical design flow rates different sources, simple to operate. will only separate relatively large droplets.

SlPM DeiJilinXMunuul. EP Y3-1315. Rev 1.1. NIIV 1993. File numc = TABS-/.DOC

Minimum droplet size separated API separators Pnmary separation, usually open to atmosphere
50 pin

Plate pack Pnmaiy separation interceptors

J pm

Hydrocarbon removal efficiencies and outlet 111 concentrations [l] No restriction Typically 50 to 100 m@. However very dependenton droplet size in feed No restriction. Typically 40 lo 100 performance will m@. However very depend on droplet size dependent on droplet dislribulion. size in feed. Inlet concentration Typically 80 l o 90% should typically be lower removal, 20 lo 30 m9/1 in outlet stream. than 400 mgA to achieve 40 m@ outlet However very spec. However, dependent on droplet performance will size in feed. depend on droplet size distnbution

Recommended hydrocarbon Inlet concantrations

Solids handling

Use of chemicats

Advantages

Disadvantages

Solids will settle on bollom. May be continuously removed by scraper bars. Solids should be \lot normally removed before entenng JSed the actual plate pack lo avoid blocking plates.

Large space requirements Allows oxygen ingress Superseded by CPI plate pack interceptor desgn Plates can block with solids or fouling Plate pack spacing should be higher where solids or fouling IS expected which reduces separation performance Performancedetenoratesat non design conditions Oil reject ports may block with light solid materials High solids concentration may result in erosion

Hydrocyclones

Can be used as pnmary water lrealment provided solids and hydrocarboi concentrations are acceptable May be used as coalescers if relect stream closed Can be used as pnmary water treatment

3tot5pm

Rotary hydrocyclones

to 10 pm

(typically) as feed mus be low pressure and degassed

own lo 2 pm

Low solids concentration acceptable, exits with water phase. High solids concentration may result in erosion, especially for high pressure drop applications. Can use special liners to minimisf erosion. Inlet concentration Typicalty 85 lo 95%. Low solids concentration Uot normally should typically be lower Typically 15 to 25 acceptable. Not as JSed than 600 m@ to mg4. However very subject lo erosion as a achieve 40 m@loutlet dependent on droplet static hydrocyclone. spec. However, size in feed. However solids may performance will accumulate. reducing depend on droplet size separation performance. Idistribution. I ITypically should be ITypically 90 lo 98% lCan handle up to 5% Vot normally ised

Good pnmary separation device which can degas liquids, remove solids and slugs of hydrocarbons Compact gravity separation device StandardShell CPI design available which supersedes API desiqns Compact robust design especially for \lot normally )sed, however in onshore applications Can be designed for high pressure and installedupstream of ,ome cases control valves Modular design allows leoilers have capacity 10 be increasedas required New mproved the designs improve separationperformance ,eparation at lower pressure drops )erformance Compact, separation efficiency higher than static hydrocyclones designs and more constant over a range ot operating conditions Performancelies between hydrocycloneand centrifuge,however more compact and requires less power than centnfuges Excellent separation performance Can separate water, hydrocarbons and solids Performancestable over a wide range of operating conditions

Added complexity of rotating mechanical equipment No Shell installations to date

I

High weight space and cost compared lo hydrocyclones especially for large water flows Added complexity of high power consumption Low capacity per individual unit (=lo0mVh) Examples where poor performance experienced Very dependent on water chemistry and steady operation Field trials recommended Chemical trials required to optimise performance
only be used at low pressure Relatively

rotating mechanical equipment Can

flotation Hydrocarbonslugs will result in poor separation.

3eoilers and Doiyelectrolytes ,hen used to work indicates otherwise mprove Ilotation Derformance
I
I

In many cases can achieve excellent performanceunder steady conditions Now available in pressure vessel configurations

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Filr numr = TABX-/.DOC

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Table 8.1.1 W i l i n g equipment summary table Page 2 of 3

I1 I Inlet urid tirifler hydrocurbon :im'entrurions rind efficiencie.\ ure typiwl only.

In miist cues performunce ujill depend on dnipler size disrributiim. U.rer.s should refer t o the equipment simimuries U I the end ifniozt equipnient .sec.riin.s i n Chupfer X t o see the runge of results ribruined in d$ferent rriuls und operuting in.rtullutims.

Equipment

Location

Minimum droplet size separated

Dissolved gas flotation

Sand and dual medie deep bed filtration

Secondary treatment, 2 to 5 pm (using ,ecommendedused in Ilocculation) :onjunction with :oagutation and ,locculation Tertiary treatment 2 pm

Recommended hydrocarbon inlet concentrations [l] Typically should be less than 500 mgl to ensure a satisfactoryeffluent.

Hydrocarbon Solids handling Use of removal efficiencies chemicals and outlet concentrations [l] Typically 80 to 90% Variable effects, should Upstream removal, 10 to 40 be avoided unless test flocculants and work indicates otherwise. polyelectrolytes mgl in effluent. used. Solids removed. Should be less than 50 mg/l in feed to ensure adequate length 01 filtration cycle.

Advantages

Disadvantages

In many cases can achieve excellent performanceunder steady conditions. Flotationaction is gentle enough to be used with upstream llocculation.

Without upstreamCoagulationand flocculation induced gas IlOtatlOn is prefened. Relatively large and heavy equipment.

Crushed nut Tertiary treatment shell media filters and oleophilic media filters Cartridge filters Polishing treatment. 3fIen used as guard fitters lor water injeclion. Polishing treatment

Precoat filtration Membranes

Tertiary treatment

Equipment large and heavy. Media Can be louled by high hydrocarbon concentrations in feed or waxy or fouling hydrocarbons. Requiresadditionaltanks to store both clean and dim/ backwash I I I I I ]water. 12 pm Ilnlet oil content should IRemoval of 95% of ISolids removedby !Not typically ]High quality water effluent. usually suitablelEquipmentlarge and heavy. Tends 10 be slightly heavier than equivalent dual lorwater injection. More resistant lo be less than 150 mgl. particles greater than filtration. Solids removal used. HCI media system. Each filter has an Some experience to 200 2 pm. Typically < 5 not as effective as dual iniection used in hydrocarbon fouling than other media mgn. mgl in effluent. media filters. some locations filters, Can be backwashed with dirty associatedpump lor backwashing to prevent water. Do not need vessels lor clean and increasing maintenance requirements. formation 01 iron dirty backwash water. Lower volume of precipitates, back wash water produced. Only suitable lor polishing duties due lo High quality water eflluent, absolute Not normally Hydrocarboncontent Solids removedby Typically 2.0 pm, Can be absolute particle size ratings available. Compact cost of cartridge replacement. used. should be very low ( 4 rated down to 0.6pm. filtration. Solids level down to 0.6 pm equipment design. mgl) to avoid frequent Typically < 1 mg4 in shoukd be low to avoid cartridge replacement. effluent. frequent cartridge I replacement I I I IDown to 2 ptm IFilter pre-coat ]High quality water effluent Used in water IRequirescontinuousdosing of tiller aid llnlet oit content should IRemoval of 98% of )Solids removed by Facilities must be providedfor storage treatment plants for stream raising be lower than 15 mgl. particles greater lhan filtration. Solids should required. and preparation01 filter aid, and systems. 2 pm. Typically < 1 typically be less than 5 disposal of lilter aid cake after filtration. mgll in effluent. mqlt. As low as possible if Typically 10 mg/l in Solids will not pass Alcoa Petrolux Potentially very compact size. Good Not sufficientlydeveloped. Membrane Depends on membrane type. loulingis likely. effluent. through membrane. uses coagulant effluent quality. New improved membranes fouling reduces flux rates. Cleaning Typically down to at Should be minimisedto to improve being developed. systems need to be improved and

Inlet oil content should Removal of 98% of be lower than 30 mgl. particles greater lhan Some experience to 100 2 pm. Typically < 5 mgh. mg4 in eflluent.

I

Upstream High quality water effluent. typically coagulant and suitable lor water injection. llocculantsoRen used to improve performance.

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Table 8.1.1 Deoiling equipment summary table Page 3 of 3

11 I lnler und outler hydrtnurbrm concenrrutiims und efticiencies ure ryicul only. In most u s e s perjiirmunce will depend 1 1 1 1 droplet size drsiriburion. Users should reJer to the equipment sunimuries ut the end ofmo.sr equipment seciiimr in Chuprer 8 10 see the runge i,fresults obruined in digerenr rriuls und operufing insrulluriiins.

8.2 Dispersed hydrocarbons - Definitions
8.2.
8.2.1.
DEFINITIONS Deoiling efficiencies
The performance of deoiling equipment is often expressed as an efficiency. The two most common definitions are hydrocarbon removal efficiency and process efficiency.

Hydrocarbon removal efficiency is a simple percentage efficiency relating the feed and product oil concentration. It does not consider the quantity of the product and reject streams, only the quality of the product compared to the feed.
Hydrocarbon removal efficiency (%): EOil = 1-

(

- x 100

3

Eq. 8.2.1

The process efficiency takes the process flow rates into consideration and will thus indicate a poor efficiency for a process which generates a large reject stream.

Process efficiency (%):

Ep=

( ~L~~~
1--

)x( 1-R)xlOO

Eq. 8.2.2

Where:

R
CF C , QF 0 , Q ,

= reject ratio =
=

= oil in water concentration in feed (mgll)
= product flow rate (mYh) = reject oil stream flow rate (mVh)

[?)

= feed flow rate (m3/h)

oil in water concentration in product (mg/l)

The major deficiency of these definitions is that they do not consider the size distribution of the dispersed hydrocarbons in the feed stream. Thus, while a particular class of deoiling equipment may have 100% hydrocarbon removal efficiency for 50 pm droplets, it may have a 0% hydrocarbon removal efficiency for 5 pm droplets. Thus these efficiencies are only a measure of deoiling performance at a particular droplet size distribution. The expression for hydrocarbon removal efficiency highlights an obvious, though often overlooked principle of water deoiling. No deoiling equipment can guarantee an absolute effluent quality, only a relative reduction in hydrocarbon concentration. This leads to the following important guidelines for the design and operation of deoiling equipment.

No matter how efficient the deoiling equipment, in most cases high hydrocarbon concentrations in the feed will result in high hydrocarbon concentrations in the outlet. When trying to improve overall deoiling performance, it may be easier to lower the inlet hydrocarbon concentration (by improvements to upstream equipment) rather than striving for marginal improvements in the performance of the deoiling equipment alone.
Higher overall removal efficiencies may be obtained by operating deoiling equipment in series. For example, two deoiling stages in series operating at a relaxed 80% efficiency will have the same overall performance as a single stage operating at a 96% efficiency. These guidelines are discussed further in Chapter 7, Equipment Selection and System Integration.

.

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8.2 Dispersed hydrocarbons - Definitions

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8.3 Dispersed hydrocarbons - Coalescers
8.3. 8.3.1.

COALESCERS
General
The performance of most deoiling equipment for the removal of dispersed hydrocarbons is strongly influenced by the size of the hydrocarbon droplets in the feed stream with larger droplets being easier to separate. Coalescers are devices designed to promote the coalescence of small hydrocarbon droplets into larger droplets. Many coalescers do not actually separate hydrocarbons from water, however they aim to improve the separation performance of downstream equipment by increasing the hydrocarbon droplet size in the feed to these downstream units. There are a wide range of coalescing devices available from equipment suppliers. However, in general all coalescing devices are based on the principle of increasing the probability of contact between the dispersed hydrocarbon droplets. If the conditions are suitable, the droplets can then coalesce to create larger droplets. By definition, a coalescing device does not separate the hydrocarbon and water phases, merely alters the droplet size distribution. In practice, many coalescing devices are packaged as combined coalescers/separators.

8.3.2.

Definitions
The following equation may be used to define the coalescing performance of a coalescing device. It calculates the percentage change in the volume of hydrocarbon contained in droplets smaller than a nominated cut-off diameter. The cut-off diameter of interest is usually selected on the basis of the minimum droplet size required for the efficient operation of downstream separation equipment. For example, if a plate interceptor type separator was to be used downstream of a coalescer, a useful cut-off diameter would be in the order of 40 pm, as illustrated in equation 8.3.1.
% < 40,

Coalescing efficiency =

- % < 40,

% < 40,

Eq. 8.3.1

Where:

Yo < 40,

=o / o of hydrocarbon volume in droplets less than 40pm in the feed

% < 40, = % of hydrocarbon volume in droplets less than 40pm in the product

8.3.3.

Performance variables

8.3.3.1. Hydrocarbon droplet size
Trial work has indicated many coalescing devices will have a minimum cut-off diameter below which coalescence will be relatively ineffective. This is particularly apparent for relatively coarse coalescing devices such as packings, spirals or serpentine paths which do not exhibit any significant coalescence effects on particles smaller than 40 pm. Better coalescing performance is exhibited by coalescers using filtration type coalescence (deep bed or cartridges) where significant coalescence of droplets smaller than 10 pm occurs.

8.3.3.2. Inlet hydrocarbon concentration
The performance of many coarse coalescing devices will usually improve with increasing inlet hydrocarbon concentration. The higher hydrocarbon concentration increases the probability of collisions between hydrocarbon droplets which is the first requirement to allow coalescence to occur.

8.3.3.3.

Emulsion stabilisers/destabilisers
The coalescence process is the opposite of emulsification. Thus any factors that tend to stabilise emulsions will reduce the coalescence performance. This may include stabilising surfactant chemicals, fine solids and the other emulsion stabilisers discussed in Chapter 3.0. Conversely, processes which destabilise emulsions will improve the coalescing performance, such as deoiling chemicals that increase the interfacial tension between the phases. Emulsion destabilisers are also discussed in more detail in Chapter 3.0. The effect of surface active chemicals on the surfaces of coalescing elements must also be considered.

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8.3 Dispersed hydrocarbons - Coalescers
Treatment chemicals such as corrosion inhibitors may coat the surface of the coalescing media with a film that interferes with the coalescing action.

8.3.4.

Installation/Configuration
Process location
The function of a coalescing device is to coalesce small dispersed hydrocarbon droplets into larger droplets. Thus coalescing devices should preferably be located immediately upstream of the separation equipment that is to take advantage of the larger droplets created by the device. Potential sources of shear forces between the coalescing device and the separation equipment should be eliminated or minimised. In most cases, the coalescing device will be packaged as an combined coalescer-separator, such as vessels or tanks with coalescing devices on the inlet stream plate pack separators.

8.3.4.1.

8.3.5.

Coalescer designs

8.3.5.1. General
There are a wide range of coalescer designs available from vendors. The broad classes of coalescer design are introduced in the following discussions, while additional detail on a range of specific coalescing equipment is included in Appendix G. Also included in Appendix G are figures illustrating the coalescing performance of five of the designs which were tested at the Orkney Water Test Centre in 1991. Table 8.3.1 summarises the performance of coalescers from a range of trials and installations. For more detailed information the user is referred to the full OWTC report (EP 92-0942) and the reports EP 891365 (Ref.2.14.2.c) and EP 89-1366 (Ref.2.14.2.c) which investigate the performance of a range of coalescer elements.

8.3.5.2.

Coarse coalescers
Coarse coalescers are robust designs used to promote the coalescence of relatively large hydrocarbon droplets. They do not have a significant coalescing effect on droplets smaller than 40 pm. Coarse coalescers have the advantage of being relatively cheap and may often be designed to be tolerant of solids in the feed stream. They are suitable for relatively simple coalescing duties upstream of coarse separation equipment such as skimming tanks and separators. Examples of coarse coalescers includes the Knitmesh DC coalescing mesh, MPE SP Pack, Monosep Spiralsep and various types of structured packings. Plate pack interceptors can also be considered a form of coarse coalescer.

8.3.5.3.

Fine coalescers
Fine coalescers have a relatively dense coalescing media which can give good coalescing performance for small droplets. They are typically packaged into cartridge type designs similar to cartridge filters. The flow is normally from the inside of the cartridge to the outside, ensuring the fluid velocity through the coalescing media decreases as it passes through the cartridge. The coalescing media is normally oleophilic, allowing the hydrocarbon droplets to "wet" the media, encouraging coalescence. The outer later of the cartridge may be hydrophilic to encourage the release of the coalesced droplets. The potential drawbacks of cartridge type coalescers is that solids in the feed stream will tend to block the element and due to a relatively low capacity per coalescer element number of elements required for large water flow rates may be prohibitive. Examples of fine coalescers include cartridge type designs available from Knitmesh, Pall, Peco, Plenty Metro1 etc.

8.3.5.4.

Media bed coalescers
Media bed coalescers are also a form of fine coalescer, using the flow through a media bed to promote coalescence of dispersed droplets. Some designs rely on oleophilic media or oleophilic treatment chemicals to improve the coalescence performance.

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8.3 DisDersed hvdrocarbons - Coalescers
The coalescing performance of a media bed coalescer design can be very effective and they have the advantage that solid particles are filtered from the feed stream and can be removed from the filter bed by backflushing. However media bed filters are relatively large and heavy.

8.3.5.5.Hydrocyclone coalescers
Hydrocyclones may be operated in a coalescing mode by blocking off the hydrocarbon reject port, forcing the hydrocarbon core in the centre of the hydrocyclone to exit with the water stream. The centrifugal forces force the dispersed hydrocarbon droplets into close contact in the core of the hydrocyclone, promoting coalescence. Trials at the OWTC indicated relatively good coalescing performance, especially when a recycle stream was used or two hydrocyclones were operated in series. KSLA also noted this during hydrocyclone trials.

8.3.5.6.Hydraulic coalescence
In some cases, hydraulic coalescence could be considered an alternative to the mechanical coalescers discussed in the preceding discussions. Hydraulic coalescence can be achieved by contacting the water stream containing dispersed hydrocarbons with a suitable coalescing hydrocarbon stream, such as a product crude oil stream or even a dedicated recirculating hydrocarbon stream. A suitable hydrocarbon stream should be selected on the basis of low solubility in water, a high density difference from the water stream and good separation characteristics. The presence of the additional hydrocarbons droplets of the coalescing hydrocarbon steam will increase the probability of collisions between dispersed hydrocarbon droplets and encourage the coalescence of the original dispersed hydrocarbons droplets into the coalescing hydrocarbon phase. By avoiding excessive shearing forces, the bulk water and hydrocarbon phases should be relatively simple to separate. The water phase with residual hydrocarbons can then be passed to normal downstream deoiling equipment. After the hydraulic coalescence the overall hydrocarbon concentration remaining in the water should be lower and the dispersed hydrocarbon droplets should have a larger mean diameter. In addition to coalescing dispersed hydrocarbons, a suitable solvent may also be able to remove dissolved hydrocarbons. This is the basis of the extraction process discussed in section 9.7.

8.3.5.7. Pipeline coalescers
Many systems containing dispersed hydrocarbons will naturally coalesce given sufficient residence time and appropriate mixing energy to promote coalesce without shearing. This gives rise to the concept of pipeline coalescence, using the residence time and natural turbulence in a pipeline to promote coalescence. Pipeline coalescers have been installed at only a few locations. One example is in Nigeria, consisting of 150 meters of 4 inch piping and 365 meters of 6 inch piping, with residence times of 1 minute and 6 minutes respectively and a pressure drop of 1.5 bar over the system. The average separation efficiency of the system was estimated at about 40%. Design guidelines for pipeline coalescence systems are given in section A.2 in Appendix A. Pipeline coalescence systems could potentially be enhanced by the addition of a separate coalescing phase as discussed in 8.3.5.6.

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PuKe 8-3-3

Location

Equipment

USA, Shell Western E 8 P, Kemridga productiondivision OWTC

SP Pack insidf skim tank. Coarse coalescer Knitmesh Dusec, line coalescer

Field trial or installed Inlet Deta equipment hydrocarbon date of equipment installatlon concentration in brackets) (mgn) istalled equipment (1990). 1990 184 to 433 quipment tested with and Typically 280 rithout chemicals (Reverse mulsion breaker - REB) quipment testing centre 1991 Tested at 50,100.400 and

-

Outlet concentration (mgn) Without REB 190
Wifh RE8 - 7 32

Hydrocarbon removal efficiency Without REB 32%

Solids handling

Use of chemicals

Comments

Relerence

OWTC

Sulzer Mellapack. coarse coalescer

quipment testing centre

Spiralsep, coarse coalescer
SlPM D e s i l m ~ Munuul. EP

quipment testing centre

With REB 53% Not applicable for coalescer lor coalescer coalescing abilih, used 600 without separato Nithout separator when solids present. Though1 to be due to solids stabilisation of emulsion. lSee comments I 1991 Not applicable Tested at Not aDDlicable ILower I Not normallv 50,100,400 and for coalescer coalescingabilih, used lor c&escer without separatoi Nithout separator when solids BM) present. Though1 to be due to solids stabilisation of emulsion. See comments Not applicable 1991 Tested at Not applicable Difficult to Not normally lor coalescer discern effect of used 50,100,400 and lor coalescer without separato Nithout separator solids due to low 800 coalescing

Solids do not appear to block pack

Better Perfonance of skim tank without SP pack was performance very poar (8% oil removal). Installing SP pack using reverse improved removal to 32%. using deoiling emulsion breaker chemicals further improved removalto 53%

2.14.2.b

performance, especiallyfor small droplets. During trials with solids coalescingperformancecontinued Summary in Appendix D to decline, suggestingpossible solids accumulationin coalescer. Performance not considered as effectivein lresh water.

-

ICoalescinaabililv lound to imDrove with increasina IEP 92-0942 hydrocarbon droplet size and concentration. Suitable as a coarse coalescer. During trials with Appendix D solids coalescing performancecontinuedto decline, suggestingpossible solids accumulation coalescer.

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Coalescingability found to improve with increasing EP 92-0942 hydrocatboon droplet size and concentration. Performance poor for low concentrationsor small Summary in droplet sizes. Suitable only as a coarse coalescer. Appendix D

Table 8.3.1 Page 1 of 2 Deoiling equipment summary table Coalescers

-

-

Location

Equipment

OWTC

OWTC

lvortoil hydrocyclone in coalescing mode, line coalescer MPE SP Pack, Equipment testing centre coarse coalescer

I

I I

Field trial or installed Inlet Date equipment hydrocarbon (data of equipment Installetlor concentration (mgtl) In brackets) Equipment testing centre 1991 Tested at 50,100,400 and

-

1991

Outlet concentration (mgh)

Hydrocarbon removal efficiency

Solids handling

Use of chemicals Not normally

Comments

Reference

800

Not applicable Not applicable Not tested lor coalescer lor coalescer without separator without separator

used

-

Australia, North Knitmesh Rankin and Goodwyn. Dusec, Peco Laboratow trials element. PleOh/ element. Fine coalescers Australia, Goodwyn platform, Laboratory trials Cobham AFG, Knitmesh Dusec, Warner Lewis, Peco. Fine coalescers

Laboratorycomparison of coalescing performance. NOTE Tests for coalescing water in condensate. NOT oil In water. Laboratorycomparison 01 coalescing performance. NOTE: Tests for coalescing water In condensate, NOT oil in water.

-

Tested at Not applicable Not applicable Lower lor coalescer coalescing ability 50,100,400 and lor coalescer without separator without separator when solids 800 present. Thought to be due to solids stabilisation01 emulsion. 1988 Tested with loo0 Not applicable Not applicable Not tested ppm condensate for coalescer for coalescer in water reed without separator without separator stream

Not normally used

Found to give relativeiy good coalescing performance. An optimum throughput must be found which promotes coalescence but does not incur droplet shear. Coalescence improved when the recycle to the cyclone was increased. Coalescing ability found to improve with increasing hydrocarbon droplet size and concentration.Effect 01 solids considered to be due to emulsion stabilisation by solids. Suitable as a coarse coalescer.

EP 92-0942 Summary in Appendix D EP 92-0942 Summary in Appendix D

-

7C

1989 Tested with loo0 Not aDDliCable Not aoolicable Not tested .. ppm condensate lor coalescer lor coalescer without separator without separator in water

I

1

1

Re12 14.2.d Range 01 experiments investigaingcoalescing01 dispersedwater in condensate. For this application Knitmesh gave better performance than Peco elements. Plenty element gave paor performance. Corrosion inhibitor appeared to alter coalescer media properties01 all elements and reduce performance. Corrosion Five different coalescina elements were tested lor Re1.2.14.2.c inhibitor lound to the removal 01water droplets from condensate hinder the The Knitmesh Dusec and Alan Cobham C6-1450coalescing M were found to be the best performers Corrosion lability inhibitor reduced the performance01 all Corrosion inhibitor lound to significantly hinder the coalescing ability.

Table 8.3.1 Page 2 of 2 Deoiling equipment summary table Coalescers

-

1

-

8.3 Dispersed hydrocarbons - Coalescers

E HAS BEEN INTENTIONALL

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SlPM Deoilinl: Munual, EP 93-1315. Rev 1.1. Nov 1993, F i k nome = 803COAL.DOC

8.4 Dispersed hydrocarbons - Flocculation
8.4. 8.4.1. FLOCCULATION General
Most deoiling processes for the removal of dispersed hydrocarbons are strongly influenced by the size of the hydrocarbon droplets in the feed stream, with larger droplets being easier to separate. Flocculation is the process by which small droplets are grouped together to form a collection of droplets known as a floc. The floc will have a larger effective diameter and thus can be more readily separated by suitable deoiling equipment. Flocculation differs from coalescence in that the individual droplets forming the floc do not necessarily coalesce into a larger droplet but join together as an agglomeration. Solids may also be captured in the structure of the floc. Flocculation is typically achieved in two stages, coagulation and flocculation. 8.4.1.1. Coagulation Coagulation is the process by which suspended solids and hydrocarbons droplets in the feed stream are combined together to form larger agglomerated microflocs. This agglomeration is assisted through the addition of a coagulant, typically ferric chloride, aluminium sulphate (alum) or ferric sulphate. The metal ion from the coagulant will precipitate as a solid hydroxide which acts as a seed for the formation of the microflocs. The precipitation of the metal salt requires the water to have the correct pH, typically from 5 to 9 in fresh waters and a narrower range for saline waters. Adjustment of the pH before coagulation may be required.

8.4.1.2.

Flocculation After the coagulation stage the water passes to the flocculation stage. Flocculation is the process by which the initial microflocs formed by coagulation are agglomerated into larger flocs. The flocculation procedure is assisted by residence time and gentle agitation. Polyelectrolytes (known as flocculants) are usually added to improve the flocculation process. These are long chain, water soluble polymers with excess electrical charges along their length which help to gather the microflocs into larger flocs. The type of flocculant to be used is dependent on the characteristics of the water and suspended droplets and solids and is established through laboratory tests. Flocculants are typically used in dosages of 0.5 to 10 mg/l. Where minimal weight or space are important, serpentine path flocculators can be used to achieve flocculation in a relatively compact design. A jar test procedure for testing the effectiveness of coagulants and flocculants is presented in the reference "Standard practice for coagulation-flocculation jar test of water", ASTM D 2035-80, Ref Ref.l.05.3.b.

8.4.2.

Floc separation
The coagulation/flocculation process on its own does not remove dispersed hydrocarbons or suspended solids from water, merely concentrates these impurities into larger, more easily separated flocs. A number of separation processes may be used downstream or in combination with the flocculation process.

8.4.2.1.

Filtration Coagulants and flocculants are often used to aid filtration. As well as aiding the formation of flocs the flocculant will improve the adhesion of the flocs to the filter media. Typical dosage rates are 0.5 mg/l of coagulant (e.9. ferric chloride) and 0.5 mg/l of flocculant. For filtration duties, coagulants and flocculants are often simply injected directly into the process piping upstream of the filters. In-line mixers can be used to ensure quick dispersion of the chemicals. Due to potential interaction of the chemicals, coagulant and flocculant should not be injected at the same point. Coagulant should be injected as far upstream as possible to give the coagulant sufficient time to form microflocs without interference. Sources of shear forces such as control valves should be avoided, especially after the addition of the flocculant. Flocculation performance may be improved by use of a serpentine flocculator upstream of the filters.

SIPM Droiling Mrmunl. EP 93-1315, Rev 1.1. Nov 1993, F i k nnmr = XO4FLOC.DOC

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8.4 Dispersed hydrocarbons - Flocculation
8.4.2.2. Flotation
The flocs formed by flocculation may be removed by dissolved gas flotation. The induced gas flotation process is not normally used for flocculation/flotation as the higher shear forces generated by the induction process in the flotation cells will tend to break the flocs.

8.4.2.3. Sedimentation
Flocculation/sedimentation is widely used for the removal of suspended solids. The agglomerated flocs of particles will settle at a higher rate than the individual solid particles.
The sedimentation process can be applied to the removal of dispersed hydrocarbons if there are sufficient solid particles present to give the flocs of hydrocarbons and solids a negative buoyancy. Alternatively weighting agents such as active silica can be added to improve the settling characteristics of the flocs.

8.4.3.

Operation considerations

8.4.3.1. Overdosing of chemicals
Overdosing of chemicals should be avoided, both to minimise chemical consumption and to avoid operating problems. Overdosing of flocculants may result in "mudbatling" of filter media. Overdosing of coagulants may result in the coating of downstream equipment with metal ion precipitates.

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8.5 Dispersed hydrocarbons - Skimming tanks and vessels
8.5. 8.5.1.
SKIMMING TANKS AND VESSELS Introduction
Skimming tanks or vessels (collectively described as “skimmers”) are simple gravity based separation equipment, designed for the continuous separation of hydrocarbon droplets from water. Skimmers are often used to provide surge capacity, ensuring a relatively stable flow to more sensitive downstream separation equipment and allowing provision for the removal of large slugs of oil which may ovewhelm downstream equipment. Skimmers can be either vertical or horizontal designs. In vertical skimmers the dispersed hydrocarbon droplets must rise upwards against the downward water flow while in horizontal skimmers the dispersed hydrocarbon droplets rise perpendicular to the horizontal water flow. Horizontal skimmers are generally more efficient as the hydrocarbon droplets do not have to flow counter-current to the water flow. However vertical skimmers may be preferred in the following situations. Where significant quantities of sand or solids particles have to be handled. Vertical vessels can be more efficiently designed for the collection and removal of accumulated solids. Where large surges in liquid levels are likely. For a given residence time a vertical vessel will have a larger distance between operating and shut-down liquid levels, minimising the risk of accidental high level shut-downs from liquid surges. Figure 8.5.1 illustrates a simple vertical skimming tank. The water stream leaves the skimmer via the discharge ring main. Hydrocarbon droplets above a critical diameter will rise against the downward water flow and can be skimmed from the water surface. Due to the large cross sectional area the skimmer can be readily designed to accommodate degassing and solids removal. In horizontal skimmers the vertical rising of the hydrocarbon droplets is superimposed over the horizontal flow of the bulk water flow. The length of the horizontal flow path must be sufficient to allow the hydrocarbon droplets to reach the hydrocarbon layer on the surface of the water.

8.5.2.

Performance variables
The performance of a skimmer is generally governed by the variables present in Stokes law. Stokes law is discussed in detail in Appendix F.
As with all separation equipment governed by Stokes law, the hydrocarbon droplet size is the most important variable affecting the separation performance. Droplet sizes should be maximised by avoiding shearing and promoting coalescence wherever possible.

Skimmers are usually sized for separation of hydrocarbon droplets of size 150 pm or larger.

8.5.3.

Installation/Configuration
As skimmers are generally designed to remove relatively large hydrocarbon droplets, they should preferably be located upstream of level control valves to minimise shearing of hydrocarbon droplets. However this will often conflict with the common requirement for degassing and a low design pressure.

8.5.4.
8.5.4.1.

Design guidelines

Basic vertical skimmers
A basic vertical skim tank such as that illustrated in Figure 8.5.1 or a vertical vessel configuration can be sized though the application of Stokes law.
Even if fitted with distributors, baffles etc., large vertical skimmers may be relatively inefficient due to internal turbulence and short circuiting. One reference suggests that 3 metres should be the maximum diameter for a vertical skimming vessel (Ref.2.6.1 .b). While larger vessels are suitable for providing surge capacity and will provide some skimming capacity, they should not be relied upon for efficient separation.

8.5.4.2.

High rate vertical skim tanks
The following reference presents a basis for the design of a “high rate” skim tank as illustrated in Figure

SIPM Deoilruji M ~ I I I I IEP ~I~ 93-1315, , Rev I 1. Nov 1993. File i i w i e = XO5SKIMT DOC

Puge 8 - 5 1

8.5 Dispersed hydrocarbons - Skimming tanks and vessels
8.5.2. The "high rate" label is based on the presumption that the internals fitted to the tank allow a higher capacity through a vessel of a given size when compared to simpler skim tank designs. "Design of a High-Rate, High-Volume OilMlater Separator", Stires, J., Journal of Petroleum Technology, November 1982, pp 2637-2644 The design philosophy for this high rate skimmer was developed from the design basis for the API separator (see Section 8.6). It is not known if this design has been used within the Shell Group.

8.5.4.3. Horizontal flow skimmers
Horizontal flow skimmers are typically horizontal cylindrical vessels or rectangular tanks sized though the application of Stokes law.

8.5.4.4.Coalescing devices
As with all separation equipment based on the application of Stokes law, the separation performance will improve if the size of the dispersed hydrocarbon droplets can be increased. If large skim tanks are to be used, consideration should be given to the installation of a simple coalescing device on the inlet stream to maximise the droplet size. The coalescing device should be a relatively simple and robust design such as a plate pack, MPE SP Pack, Natco Performax or similar. These devices are particularly suitable for fitting to skim tanks to improve throughput or separation performance. Due to the relatively large size of most skim tanks these coalescing devices can oflen be installed inside the tank itself.

8.5.5.

Control configuration

8.5.5.1.Siphon level control
The water level in the skimmer can be simply controlled using a siphon leg on the water outlet line. This maintains the level at a fixed position, allowing the accumulated hydrocarbons to be skimmed off or to exit over a weir. However, a siphon level control design will not allow the skimmer to be used as a surge vessel and will not protect downstream equipment from flow surges.

8.5.5.2.Surge vessel level control
For a skimmer being used as surge vessel, the water level will be typically controlled by a slow acting level controller. This will allow the vessel to absorb large flow surges which are then slowly passed to downstream equipment. Due to the changing levels the accumulated hydrocarbons cannot be continuously removed by a weir or a fixed skimming position. The hydrocarbons are removed by manual adjustment of the levels to allow skimming at regular intervals or can preferably be continuously removed using a floating skimmer.

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SlPM DKoihl: Munuril, EP 93-131S, RKV1.1, Nov 1993. F i k nilme = X0SSKIMT.DOC

8.5 Dispersed hydrocarbons - Skimming tanks and vessels

Oil layer

Oil skimmer

L
Elevation

Water

Plan

Figure 8.5.1 Schematic diagram of simple skim tank

Water inlet

=Blind Gas venting holes

n

oulet Grooved tee with outlet slots

Figure 8.5.2 Schematic diagram of a skim tank designed to API separator type guidelines

SlPM DeoilinfiM i m u d . EP 93-1315. Rev 1.1. Nov 1993. File minie = X0SSKIMT.DOC

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8.5 Dispersed hydrocarbons - Skimming tanks and vessels

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SIPM Deoilinji M(iiruci1.EP 93-1315. Rev 1.1. Nov 1993. File minw = 8OSSKIMT.DOC

8.6 Discharge caissons
DISCHARGE CAISSONS 8.6.1. Introduction
Most offshore platforms discharge waste water through a caisson suspended from the platform and extending below the water surface. Although primarily a conduit for water disposal, the caisson can also serve the following functions. The caisson can be sized to allow the separation of large hydrocarbon droplets from water. Although the water reporting to the caisson should have been treated to the required environmental discharge quality requirements, the caisson provides a location to capture any accidental hydrocarbon discharges before they enter the environment. The caisson can provide an alarm or shut-down point in the event of accidental hydrocarbon discharge to the caisson. The disposal caisson must not be considered as an integral part of the water treatment system. Its function is to act as a back-up device which will help minimise the potential for any large accidental hydrocarbon discharge in the event of failure of upstream equipment. At the time of writing there is no detailed information available on the process design or operation of caissons. Quiescent zone
Flowing zone

8.6.2.

Design guidelines

8.6.2.1.Hydrocarbon droplet size
Caissons typically have an inside diameter in the order of 600 to 1200 mm. If possible the diameter should be set on the basis of Stokes law to allow a hydrocarbon droplet of 150 pm to rise against the downward flowing water. This may not be practical for caissons with high discharge flow rates such as when disposing of large quantities of produced water and in many cases the diameter of the caisson may be set by structural considerations.
Figure 8.6.1 Skim pile

Oil risers

n7wmP

8.6.3.

Caisson internals
lnternals can be fitted to improve the hydrocarbon separation performance of a disposal caisson. However, with the increased complexity of upstream deoiling equipment (e.g. hydrocyclones followed by degassing tanks capable of capturing hydrocarbon slugs), the use of caissons incorporating internals and oil recovery systems has declined.

8.6.3.1. Skim piles
The skim pile design is illustrated in Figure 8.6.1. The design provides a series of baffles which assist the separation of hydrocarbon by; Providing quiescent areas under the baffles with minimum net downward water velocity. This allows small droplets to be collected. The plates minimise the actual distance that a droplet has to rise before it will intsrcept a surface and be collected.

8.6.3.2.SP Piles
MPE market a caisson design fitted with a number of SP Pack coalescing packs to improve the separation performance.

SlPM Droiling Mnuunl. Et' 93-1315, Krv 1. I .

Nov 1993, Filr

II(IIIIY =

XO6SKIMP.I)OC

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8.6 Discharge caissons
8.6.3.3. Closed caissons
Caissons can be designed with a closed bottom with the level inside the caisson controlled by a siphon leg. A closed caisson reduces the effects of wave motion and maximises the water residence time in the caisson, allowing for better removal of accidentally discharged hydrocarbons. Provision would have to be made for the removal of accumulated solids from the bottom of the caisson.

8.6.4.

Operational considerations

8.6.4.1.

Wave action
The design of the caisson will only operate satisfactorily during periods of relatively low wave action. As wave height grows, the caisson will be subject to a piston pumping action and will be unlikely to achieve any significant separation.

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SIPM DroilinK Umuctl. EP 93-1315, Rev 1.1. Now 1993, File nome = XO6SKIUP.DOC

8.7 Dispersed hydrocarbons - API separator
8.7. 8.7.1. API SEPARATOR Introduction
API separators are gravity type separators for onshore installations, designed according to principles established by the American Petroleum Institute (API). Although the design has been largely superseded by alternative designs (particularly the Corrugated Plate Interceptor (CPI)), there are a large number of existing API interceptors remaining in use within the petroleum industry. As the API separator is a well established design it is only discussed briefly in this section. Additional information on the design and operation of the API separator can be obtained from the references in the Bibliography.. A typical API separator consists of two basic sections, the inlet section and the oil-water separation channels. The body of the separator is generally constructed from concrete. Figure 8.7.1 illustrates a typical design. Inlet section The inlet section of the API separator consists of a pre-separator flume, trash rack, oil skimmer and forebay. The pre-separator flume has two functions, the reduction of flow velocity and the collection of easily separated hydrocarbons. Velocities in the flume are in the order of 0.05 to 0.10 m/sec, with a 1 to 2 minute residence time. The trash rack is a coarse screen used to remove sticks, rags, stones and other debris that would interfere with the downstream equipment. It typically consists of inclined bars spaced on 25 mm to 50 mm centres. Easily separated hydrocarbons will collect on the surface of the water in the inlet section and will be retained by a retention baffle. Skimming equipment is provided upstream of the retention baffle for the removal of the collected hydrocarbons. SeDaration section After the inlet section the water flows into the separator channels. Shut-off gateways are provided at the inlet to each channel to allow individual channels to be isolated if required. The water passes through a velocity head diffusion device which is designed to reduce flow turbulence and to distribute the flow evenly across the separator channel. Vertical slot baffles are generally used as the diffusion devices. Once in the separation channel, the flow is stable and allows the separation of hydrocarbons and solids from the water according to Stokes law. Hydrocarbons collect on the surface of the channel where they are retained by a retention baffle and removed by an appropriate skimming device. Solids will settle to the bottom of the channel. A mechanical scraper is usually provided for moving the sludge along the bottom of the separator channel to a sludge collection point. Parallel plate interceptor The parallel plate interceptor (PPI) is basically an API separator with the separation section fitted with long cross flow parallel plates to improve the separation efficiency. The concept of the PPI eventually lead to the development of the more compact and efficient Corrugated Plate Interceptor (CPI) design which superseded both the API and the PPI variation of the API.

8.7.2.

Performance variables
The separation characteristics of an API separator are governed by Stokes law. The theory of Stokes law is discussed in Appendix F. In general the API separator is designed for the removal of hydrocarbon droplets larger than 150 pm.

8.7 Dispersed hydrocarbons - API separator
8 . 7 . 3 .
8.7.3.1.

Installation/Configuration
Process location The API separator is a primary separation device. It may be used as the first stage in a two or three stage water treatment plant, or for the treatment of large water flows with easily separated hydrocarbons such as drains water or ballast waters. The size and weight of the API separator design prevents its use offshore.

8.7.3.2.

Oil skimming
A number of skimming devices are available for the removal of collected hydrocarbons from the surface of the water including rotary drums, slotted pipe skimmers, horseshoe floating skimmers and self adjusting floating skimmers. These are discussed in detail in the referenced guidelines.
A modification to the rotating drum type skimmer is the use of a oleophilic film on the surface of the drum. This makes the drum more efficient at hydrocarbon skimming while minimising the quantity of water carried over with the recovered hydrocarbons. The system can be fitted to existing API separators. If required, more details can be obtained from SlPM EPD/421 (Ref. 2.03.1 .d)

8.7.4.
8.7.4.1.

Design guidelines

API separators
The design of an API separator is covered in detail in the following references. “Manual on Disposal Of Refinery Wastes, Liquid Wastes”, 1st ed, 1969, American Petroleum Institute (API), Chapter 5 and 6 “Drainage and primary treatment systems”, DEP 34.14.20.31-Gen, May 1986 Amended by Circular No.29/86, Custodian MFSH. New revision expected early 1994 (Ref..2.04.1 .e). These references give the following guidelines for the sizing of the separation channel for an API separator. Maximum horizontal velocity in the separation channel is 0.015 m/sec or 15 times the hydrocarbon droplet rising velocity (whichever is smaller). The dimensions of the separator channel should fall within the following ranges. Depth (metres): 0.9 c d < 2.4 Width (metres): 1.8 c w < 6.0 d Ratio: 0.3 < - c
W

0.5

Unless provision is made for continuous sludge removal, an allowance of 0.3 meters should be made for the accumulation of sediment on the bottom of the separator channel 8.7.4.2. Shell Parallel Plate Interceptors The design of the Shell Parallel Plate Interceptor is discussed in detail in the following references.
0

“Manual on the Shell parallel plate interceptor”, No report number, MF document (Ref.2.03.1 .a) Standard drawings, SIPM/SICM, S I4.001 and drawings referenced thereon.

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SIPM Droiliiih. Mmuol, EP 93-1315. Rev 1.1. Nov 1993, File nume = XO7API.DOC

8.7 Dispersed hydrocarbons - API separator

/

Sludge collection hoppers I Trash rack Diffusion device Sludge discharge with lead plug

/

Flight scraper chains

I

I

Flights

I

I

I

Water discharge Oil retention baffle Oil skimming pipe

'\

I

I

ELEVATION
Figure 8.7.1 API separator with two separation channels and no skimming facilities on the inlet section

EP 660715 MQ9

SlPM Deoilinji Mmuol. EP 93-1315, Rev 1.1. Nov 1993, File twne = XO7APIDOC

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8.7 Dispersed hydrocarbons - API separator

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SIPM Deniling Mmrcnl, EP 93-1315, Rev 1.1. Nov 1993, File nome = 807API.DOC

8.8 Dispersed hydrocarbons - Plate interceptors
8.8.
PLATE INTERCEPTORS Introduction
A plate interceptor consists of a pack of inclined parallel plates with the oily water flowing through the channels created between the plates. The close proximity of the plates ensures each flow channel has a relatively small effective hydraulic radius. This maintains stable laminar flow conditions through the plate pack at a higher flow rate than for an empty vessel and allows small hydrocarbon droplets to rise relatively undisturbed by turbulence.
Within a plate pack, a hydrocarbon droplet will have a forward velocity corresponding to the net water flow and a rising velocity as defined by Stokes law. The proximity of the plates ensures that the droplet only has a small distance to rise before it is intercepted by the underside of the upper plate. The collection of hydrocarbon droplets on the underside of the plate promotes coalescence and the large coalesced droplets can rise along the plate for collection. Plate interceptors are generally treated as distinct piece of separation equipment, however, in effect a plate interceptor pack is a form of coalescing device, operating by stabilising the flow and encouraging droplet coalescence on the plates. As such, the plate pack can be used in a wide range of configurations to improve separation by promoting coalescence. For example, a plate pack could be built into an existing skimming tank to assist the coalescence of the feed stream and improve the separation performance of the tank. Common alternative names for various designs of plate interceptor designs are Parallel Plate Interceptor (PPI), Tilted Plate Interceptor (TPI) and Corrugated Plate Interceptor (CPI). A Shell standard CPI design is available and is commonly used for onshore installations.

8.8.1.

8.8.2.
8.8.2.1.

Performance variables
Hydrocarbon droplet size As a gravity based separation device, the performance of a plate interceptor is broadly governed by the variables present in Stokes law (Appendix F). The dominant variable in Stokes law is the hydrocarbon droplet size and any increase in the mean hydrocarbon droplet size in the feed to a plate interceptor will improve the hydrocarbon removal efficiency. Where possible, the plate interceptor should be located in a process location with the largest possible droplet size. A typical plate interceptor will remove droplets down to the order of 60 pm.

8.8.2.2.

Plate spacing and inclination The spacing between plates is normally in the order of 20 to 40 mm. The closer 20mm spacing will remove smaller hydrocarbon droplets. However if blockage of the plates due to solids, wax deposition, scaling or fouling is possible the wider 40mm spacing is usually specified. The plates are normally aligned at 45" to 60" from the horizontal. The steeper angles are used in the presence of solids to assist their removal from the plate pack.

8.8.2.3.

Stable flow regime The separation performance of the plate pack is dependent on maintaining a stable laminar flow regime through the plates. Factors which could upset the flow regime and should be avoided include; Flow surges. There should be no rapid changes in the flow rate entering the plate pack. Obstructions. These may take the form of plate pack supports, jetting nozzles, drains etc. These should be positioned and designed to minimise any turbulence they might induce. Solids and fouling. The accumulation of solids or fouling upstream of the plate pack or on the surfaces of the plates themselves will disturb the flow pattern and upset the flow regime. The performance of the plate pack will deteriorate over time if such accumulations are not removed.

8.8.2.4.

Reynolds number One of the main criteria governing the design and performance of plate packs is the Reynolds number. Limits are imposed on the Reynolds number to ensure that the flow regime in the plate pack remains laminar.

SIPM Droilinx M(rnuci1. EP 93-1315. Rev 1.1. Niw 1993. File

Iicune

= X0XPIATE.DOC

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8.8 Dispersed hydrocarbons - Plate interceptors
It should be noted that the Reynolds number does not constrain the capacity of the plate pack, only the frontal area of the plate pack. For example, a pack with a Reynolds number restricted to 400 will require a wide frontal area, but due to the low velocity through the pack, can achieve the required droplet separation in a short pack length. A plate pack with an allowable Reynolds number of 800 can have a smaller frontal area, but due to the higher velocity through the pack will require a longer pack length for separation. The actual flow capacity, separation ability and plate pack volume of each pack will be the same. Just the aspect ratio between the pack frontal area and pack length will be different. This relationship between Reynolds number, plate pack dimensions and plate pack capacity is examined in more detail in Appendix H.

8.8.2.5. Flow configurations
There are three basic plate pack flow configurations. Down flow A down flow design is illustrated in Figure 8.8.1. The advantages of the down flow design is that the downwards flow through the pack will help sweep solids from the plate pack, minimising the potential for blockage. The disadvantage of a down flow design is that the downwards flow through the pack may disturb the upwards flowing hydrocarbon film on the underside of the plates. Hydrocarbons which are disturbed in this manner will remain in the clean water stream.

up flow
An up flow design is illustrated in Figure 8.8.2. The up flow design has the advantage that the hydrocarbon droplets and hydrocarbon film on the underside of the plates are moving in the same direction as the flow of the water. Fingers are often used on the top of the plates to allow the hydrocarbons to accumulate and coalesce before leaving the plate. Separation of the hydrocarbons and water is after the plate pack. The disadvantage of the up flow design is that the upward fluid flow will hinder the settling of solids through the pack, making the plate pack more susceptible to blockage when suspended solids are present in the feed stream. Cross flow A cross flow design is illustrated in Figure 8.8.3. The water flows horizontally across the plates and does not preferentially favour the separation of hydrocarbons or solids. The cross flow design has the advantage in that it can be efficiently packaged into different configurations. As it does not need excess space above or below the plates for the entry and exit of the water flow it can often utilise more of the available vessel volume than alternative designs. This is a particular advantage in pressure vessels, where a cross flow design can fill more of the available cross-sectional area with plates and thus minimise the overall size of the vessel.
Oily wa in

Solids Figure 8.8.1 Down flow plate geometry

'

H7Y)mmP

NOTE: Up fbw design ml recommended when adids in feed

H75m8/10P

Figure 8.8.2 Up flow plate geometry

Hydrocarbons

Y er

HIWlIP

Figure 8 . 8 . 3 Cross flow plate geometry

Puxe 8-8-2

SIPM Deoilinh. M(muu1, EP 93-1315. Rev 1.1. Niiv 1993, File nome

= X0XPIATE.DOC

8.8 Dispersed hydrocarbons - Plate interceptors
Recommended flow aeometly The following general guidelines can be used to assist the selection of a plate pack flow geometry. In the absence of other factors, the cross flow design is a good compromise offering efficient packaging, a horizontal flow path and neutral behaviour towards both solids and hydrocarbon droplets. The horizontal flow path of the cross flow design often makes it the simplest design to retrofit to horizontal separation equipment. When solids are expected the down flow configuration is often the best choice as the downwards flow keeps the solids moving and prevents blockage of the plates.

If a high solids loading is expected the up flow configuration or a cross flow configuration with the flow along the corrugations should not be used due to the risk of plate blockage.

8.8.2.6.

Corrugated plates
In a plate pack consisting of flat plates, the hydrocarbon droplets accumulating on the bottom surface of the plates will be relatively evenly distributed across the surface of the plates. This even distribution will not assist coalescence of the hydrocarbon droplets. Figure 8.8.4 illustrates the behaviour of hydrocarbons and solids in a down flow corrugated plate pack with the flow along the corrugations. The same arrangement could be used for an upflow configuration. A cross flow configuration would typically have the flow entering from the side, flowing across, not along, the corrugations.

I

Oily water feed

The rising hydrocarbon droplets will be concentrated in the concave surfaces under the corrugated plates. This accumulation in the corrugations will assist in the coalescence of the droplets and improves the separation performance of the plate pack. Solids will tend to concentrate in the troughs on the upper surfaces of the corrugated plates. Unfortunately, no information has been found which can actually demonstrate whether corrugated plates have better coalescing properties than flat plates. On this basis both flat plates and corrugated plates must be considered equally acceptable. The only constraints on the use of corrugated plates are; If solids are present the corrugations must be aligned to allow solids to move out of the plate pack without being trapped by the corrugations.

Clean water out Figure 8.8.4 Corrugated plates

HIS02(Yl??

If the flow direction is across the corrugations the allowable Reynolds number (400) is lower than if the flow is along the line of the corrugations (800).

8 . 8 . 3 .
8.8.3.1.

Installation/Configuration

Process location
Plate interceptors can be built into pressure vessels and thus can be installed at any point in the water treatment process. They are often installed as a first stage in a water treatment system, designed for removal of the bulk of the dispersed hydrocarbon before a second treatment stage. However where the process allows the plate pack should be used as far upstream as possible, upstream of level control valves and if conditions permit, even in primary separators. Figures 8.8.5 to 8.8.8 illustrate a range of possible configurations. Plate packs are often successfully used for single stage treatment of streams with large oil droplets such as deck and drains water and ballast water treatment. As with any deoiling equipment where the separation is governed by Stokes law, every effort should be taken to minimise the shearing forces and to encourage coalescence upstream of the plate interceptor.

SlPM Deoiliitl: Munuul. EP 93-1315. Rev 1.1,NIIV1993. File

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= XOXPIATE.DOC

P u p 8-8-3

8.8 Dispersed hydrocarbons - Plate interceptors
8.8.3.2. Size, Weight and Capacity
Pressure vessel based date pack desiane Due to the wide variation in potential design conditions (e.g. design pressure, solids loading etc.) and plate pack orientation it is not possible to give typical dimensions for a pressure vessel based plate pack interceptor design. Appendix H provides guidelines for the sizing of plate packs to separate a given droplet diameter. These guidelines can be combined with normal pressure vessel sizing guidelines to estimate typical sizes and weights of pressure vessel based plate pack designs for a given application. Standard Shell onshore CPI desian Table 8.8.1 gives typical sizes of the standard Shell design concrete based CPI design, suitable for an onshore installation.

Number of platepacks 4

1

16

8 8

10.1

L 6 5 . 8

Dimensions (m) W D 2.9 1.5

Capacity (mVh) 40mm 20mm Storm

Comments Single pack Single bank, 4 in row Single bank, 8 in row Double bank, 4 in each row Double bank, 8 in each row

5 . 6 10.1

4.6 4 . 6 8 . 3 8 . 3

3.5 3.5 3 . 5 3 . 5

15 60 120 120 240

240 240 480

120

30

60 240 480 480 960

8.8.4.

Design guidelines

8.8.4.1. Sizing
The sizing of plate packs for a given separation duty is discussed in Appendix H. The key criteria to be satisfied are; The Reynolds number through the plate pack should be equal or less than 800 for any flat plate configuration, or for corrugated plates where the flow is along the corrugations. The minimum hydrocarbon droplet size that can typically be separated in a conventional plate pack is in the order of 60 microns. Higher Reynolds numbers and more turbulence (up to 1500) can be tolerated if the hydrocarbon droplets are large or if a lower separation performance is acceptable. The Reynolds number through the plate pack should be equal or less than 400 for a corrugated plate configuration with the flow across the corrugations. The separation performance of the plate pack will be governed by the relative dimensions of the plate pack. These dimensions determine whether a rising hydrocarbon droplet will intercept a plate before leaving the plate pack.

8.8.4.2. Concrete based standard CPI design
Shell has a standard design for an open, below ground, concrete based, down flow corrugated plate interceptor as illustrated in Figure 8.8.8. This design is commonly used for land based installations. The design of such a CPI is covered in detail in the following documents.
0

“Drainage and primary treatment systems”, DEP 34.14.20.31-Gen, May 1986 Amended by Circular No.29/86, Custodian MFSH. New revision expected early 1994 (Ref.2.04.1 .e) “Deoiling industrial waste water. Design and operation of the “CPI” (Corrugated plate interceptor)”

0

P q e 8-8-4

SlPM Deoiliiifi M~tnuol, EP 93-1315, Rev 1.1. Nov 1993, File numr = X0XPLATE.DOC

8.8 Dispersed hydrocarbons - Plate interceptors
Report MF 81-8700, May 1981 (Ref.2.04.l.d) Standard drawings, SIPM/SICM, S14.040 to S14.047 inclusive (Feb. 81), covering general arrangements, start-up and operation, construction details, multiple bay configurations. (Included with reference MF 81-0700 above, should be updated with DEP 34.14.20.31 early 1994) These documents include example calculations, standard dimensions, and cover all civil and construction requirements for the CPI design. It should be noted that the normal capacity of the Shell standard design is based on a Reynolds number of 400.

8.8.5.

Operational considerations

8.8.5.1.

Solids handling
If solids are expected in the feed stream the design should allow for their removal. Rapidly settling solids can be allowed to settle in a stilling zone before entering the plate pack. Finer solids and sludge will settle at the bottom of the plated section. Appropriate nozzles and jetting systems should be provided for removal of accumulated solids.

8.8.5.2.

Plate pack removal In many applications the plate pack may eventually be blocked due to fouling or accumulation of solids. Provision should be made for suitable access and lifting equipment to allow the removal of the plate pack for cleaning or replacement as required.

8.8.5.3. Operating experience
Table 8.8.2 summarises the performance of plate pack interceptor designs in a range of installations and trials.

Oily produced water
Foam screen

9

I I

---i--?
Treated water

. ,

u4

Sludge

Figure 8.8.5 Multiphase separator incorporating plate pack (Skimovex)

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= X0XPLATE.DOC

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8.8 Dispersed hydrocarbons - Plate interceptors

Flow distributor
Treated water

Figure 8.8.6 Down flow plate pack Possible pressure vessel configuration (Skimovex)

HIY)26157P

-

Oily produced water

Hydrocarbons discharge

t

Treated water

Sand outlet

Sludge outlet

Figure 8.8.7 Cross flow plate pack Pressure vessel configuration (Rossmark-Pielkenrood)

-

Paxe 8-R-6

SlPM Droiling Monica/, EP 93-1315, Rev 1.1. Nov 1993, File nnme = X0XPlATE.DOC

8.8 Dispersed hydrocarbons - Plate interceptors

OUTLET WEIR

OIL SKIMMER

INLET BAFFLE

00

n o

4 OFF

CPI PACKS

EP 660714 M I S

Figure 8.8.8 Illustrative schematic of standard Shell CPI design

Location

Equipment

The Nethedands. Schoonebeck UK. North Sea. No& Cormorant platform

Fram CPI CJE tilted plate separators

Inlet Field trial or Installed Date hydrocarbon equipment (date of equipment Installation concentration (mg/l) In brackets) 150 Short field trial with small 5 mJ/h 1981 test unit. Not given Installed equipment (1982) 1993

Outlet concentration (mfl)
10 to 20

8010100

UK. North Sea, Skimovex Fulmar Alpha platform

Installed equipment (1982)

1993

5010 150

1210 to6 Typically 46

Non Corrosive Installed equipment (1978) UK, North Sea, Cormorant A platform Metal Products UK tilted plate separators UK, North Sea, Dunlin Non Corrosive Installed equipment. Includes platlorm. including Metal Products treatment of water from the Osprey development UK tilted plate Osprey development. Osprey separators results in ifalics(Os).

f

2106

2106

(Os)300 to 400

25 to 30

24 to 29
(OS) 200 to 300
. .

70% Not aiven
25%

Notknown
I

vessel

Notused
I

INo Droblems to Idate. kolids oradualk!

I Not used
INot used

Units perform relatively satisfactorily.System to be 1993 deoiling upgraded during the Forcardos terminal upgrades. questionnaire I I Performgnce is claimed to deteriorate with 11993 deoilino I

ldisposal inlection Soiids gradually foul plates

I Performance relatively poor. Water is disposed by

lincreasinqfeed concentration.

11993 deoilinn

lquestionnaire

Iquestionnai;

S f P M Droiling Munul. EP 93.1315. Rrw 1.1. Nov 1993. Filc n u m = TABX-XDOC

Table 8.8.2 Deoiling equipment summary table Plate pack interceptors

-

8.9 Dispersed h.ydrocarbons - Static hydrocyclones
8.9. 8.9.1. STATIC HYDROCYCLONE Introduction
The static hydrocyclone has rapidly been accepted as a compact and efficient means of removing dispersed hydrocarbons from water. The basic design of the static hydrocyclone is illustrated schematically in Figure 8.9.1. The water containing the dispersed hydrocarbons enters the hydrocyclone through a tangential inlet at the top of the swirl chamber. As the liquids swirl along the hydrocyclone, the centrifugal forces generated promote the separation of the hydrocarbon and water phases, with the hydrocarbon phase forming a thin core at the centre of the hydrocyclone.

Oily water feed through tangential inlet

Cylindrical / swirl chamber

section

H7rn1.1P

Figure 8.9.1 Schematic diagram of a static hydrocyclone

By maintaining a suitable pressure ratio between the clean water outlet stream and the reject oil outlet stream, the geometry of the hydrocyclone will result in the thin hydrocarbon core flowing in a reverse direction, exiting from the top of the swirl chamber. The clean water exits from the tail section of the hydrocyclone.

8.9.2.

Definitions
The following definitions are commonly used for hydrocyclones. Feed: Underflow: Reject stream or Overflow: Reject ratio (R): The oily water feed stream entering the hydrocyclone The clean water stream exiting from the tail of the hydrocyclone The concentrated hydrocarbon stream exiting from the head of the hydrocyclone though the reject port. The ratio of the reject and feed stream volumetric flow rates:

8.9.3.

Performance variables

8.9.3.1.

Introduction
The flow patterns and forces acting within a hydrocyclone are very complex and unlike traditional gravity based separation equipment cannot be simply described in terms of Stokes law. Appendix I presents a discussion of the some of the methods which can be used to model hydrocyclone separation

8.9 Dispersed hydrocarbons - Static hydrocyclones
performance. However, in general terms, the variables present in Stokes law will have a strong influence on the separation performance of the hydrocyclone and these variables are examined in detail in the following discussions. In these discussions, graphs are presented illustrating the influence of these variables on hydrocyclone ,, where ,d , is a performance. These graphs present hydrocyclone performance in terms of ,d hydrocarbon droplet size that has a 75% chance of being removed from the water stream. Thus the smaller the value of ,, d , the better the separation performance of the hydrocyclone. Reference should also be made to sections 8.10 and 8.11 which contrast the performance of the static hydrocyclone against the dynamic hydrocyclone and centrifuge. It should be noted that the results in each section were obtained under different experimental conditions and are thus not directly comparable. Although the results presented in this section and sections 8.10 and 8.11 are based on equipment trials, they are for illustrative purposes only and should not be used in isolation to predict the potential performance of a hydrocyclone. The actual performance of a particular hydrocyclone installation will be dependent on the net effect of all performance variables, particularly the size distribution of the hydrocarbon droplets in the feed to the hydrocyclone.

8.9.3.2.

Hydrocarbon droplet size Stokes law (Appendix F) illustrates that diameter is the dominant variable affecting the buoyancy of a hydrocarbon droplet. Although Stokes law cannot be directly applied to a hydrocyclone, the droplet size will have a similar effect on the buoyancy forces which cause the hydrocarbon droplet to migrate to the centre of the hydrocyclone. Thus, as the size of a hydrocarbon droplet increases, the rising velocity of the droplet increases and the droplet has a higher probability of migrating to the reject oil stream. Similarly, as the droplet size decreases, there will be a reduced probability that the droplet will migrate to the reject oil stream and an increased probability of the hydrocarbon droplet exiting with the water stream. This behaviour is illustrated in Figure 8.9.2 where it can be seen that a droplet size of 6 microns has only a 56% probability of being separated from the water stream.
110
100 80

90

70 60
50

40

30 20
10

0

0

5

10

15

20 25 30 Droplet size (pm)

35

40

45

Figure 8.9.2 Hydrocarbon droplet removal probability versus droplet diameter

As a result, it is important to maximise the droplet size reaching the hydrocyclone by avoiding shearing and promoting coalescence wherever possible. Hydrocyclones should be located close to the source of the oily water, preferably upstream of control valves. For pumped hydrocyclone installations, the feed pumps should be a low shear design. The cut-off droplet diameter for a hydrocyclone is dependant on a number of variables such as water viscosity, density differences etc. However, as a guide, it can be assumed that the current generation of hydrocyclones will have difficulty separating droplets smaller than 10-15 prn when operating at design conditions. Separation of droplet sizes in the order of 6 to 7 pm can be achieved using the latest designs of
Pujie 8-9-2
SlPM Drorlrnl: Mitriinrl, EP 93-131.5. Krv I 1. Nov 1993. File nome = XG9CYCLO DOC

8.9 Dispersed hydrocarbons - Static hydrocyclones
hydrocyclone (e.g. Vortoil K liner) if conditions are favourable (e.g. high density difference between the phases, low water viscosity).

8.9.3.3.

Flow rate
The physical geometry of the hydrocyclone is designed to generate the optimum swirl characteristics at a particular design flow rate, maximising the centrifugal separation acceleration while minimising shearing of the dispersed phase into smaller droplets. At low flow rates, separation is reduced due to lower centrifugal forces. This behaviour is illustrated in Figure 8.9.3 where it can be seen that as the flow rate is reduced, the value of d7, rises, indicating reduced separation performance. In general, to achieve satisfactory separation it is recommended that hydrocyclones are not operated below 40% of their design capacity.
20.0
17.5

15.0

E, ; ;12.5
u
IC.

10.0
7.5

5.0

0

10

20

30

40

50

60

70

80

90

100

110

120

% of design flow capacity

Figure 8.9.3 Variation in hydrocyclone performance with flow rate (% of design capacity)

At some point above the design flow capacity the performance of the hydrocyclone will deteriorate. This deterioration can be due to a number of factors. At higher flow rates more shearing may be experienced in the hydrocyclone, reducing droplet size and separation performance. As flow rates increase, the pressure drop across the hydrocyclone will increase until eventually the available feed pressure is not sufficient to drive the reject stream out of the hydrocyclone. Even before this point is reached, the increased pressure drop may lead to gas breakout in the hydrocarbon core, upsetting the performance of the hydrocyclone.

8.9.3.4.

Inlet hydrocarbon concentration Hydrocyclones can tolerate large surges in oil concentrations. Normal hydrocarbon removal efficiencies have been observed with hydrocarbon concentrations in the order of 12,000 mg/l hydrocarbons. However, it must be recognised that the hydrocarbon removal efficiency is simply a ratio between the inlet and outlet hydrocarbon concentrations. Thus as the inlet concentration rises, the outlet concentration will also rise. Figure 8.9.4. illustrates a number of effects of higher feed concentrations on hydrocyclone performance. Firstly, as shown by the points marked by squares, as the hydrocarbon content of the feed increases the separation efficiency of the hydrocyclone also increases. The reason for this improvement is apparent from the figures in the small table included within the figure. It can be seen that as the hydrocarbon concentration increases, the average droplet size also increases. This increase in droplet size is due to the higher chance of droplet collisions and coalescence at the higher hydrocarbon concentrations. The hydrocyclone can more readily remove the larger droplets, hence the separation performance of the hydrocyclone improves. Secondly, the bars on Figure 8.9.4highlight the relationship between separation efficiency and outlet concentrations. It can be seen that even though the separation performance of the hydrocyclone improves with the increasing feed concentration, at a feed concentration of 500 mg/l the outlet concentration has exceeded the desired concentration of 40 mg/l. At a feed of 2200 mg/l, the outlet

8.9 Dispersed hydrocarbons - Static hydrocyclones
concentration has increased to over 90 mg/l. This simply highlights the point that the hydrocyclone will not guarantee a fixed outlet concentration, high inlet concentrations will lead to high outlet concentrations.
100 -

8
Y _.

90

80 ‘3 70 --

-* - /
I I I

FI’

;/*

/CJ---

----- 100 -- 80
r-

-.- 60

I

! .

E

50 -40 --

ccncmtrabom for constant shear rate 13pm 0 50 mg‘l 52pm (B 900 mg‘l M P m 8 203 mg‘l 66pm (D 1500 mgh

.E
c
L

i5

30 -- I I 20 -- I

-

_ _ _ _

-

-- 60

E

_ _ _- - 4 0

8 ..c m

E

I

-- 20 a
0

x

- - - - Efficiency required to
achieve 40mg4

0

Oil removal efficiency actually achieved

Actual discharge oil concent ration

Figure 8.9.4 Variation in hydrocyclone performance with feed concentration at constant shear

Secondly, it can be seen that the efficiency of the hydrocyclone tends to increase with increasing hydrocarbon feed content. This is to be expected as the larger droplet sizes with the higher hydrocarbon concentrations will be easier for the hydrocyclone to separate. Eventually the removal efficiency gains become marginal with increasing feed hydrocarbon content. This behaviour is thought to represent a balance between the coalescing forces of the higher hydrocarbon content and the shearing forces being exerted on the large hydrocarbon droplets inside the hydrocyclone.

8.9.3.5. Reject stream ratio
The discharge rate of the reject stream must be adjusted to ensure that the central hydrocarbon core is removed from the hydrocyclone. Below a minimum reject ratio, the efficiency of the hydrocyclone will be poor as the reject stream flow rate will be too low to purge the hydrocarbons from the hydrocyclone and some hydrocarbons will be discharged with the water stream. Figure 8.9.5 illustrates the a typical relationship between oil removal efficiency and reject ratio. As the reject ratio is increased, the efficiency of the hydrocyclone improves. Higher reject ratios will achieve marginal improvements in hydrocarbon removal efficiency, however this is at the expense of a larger volumetric flow rate of reject stream, hence a lower process efficiency. The optimum reject ratio will be dependent on the particular operating conditions of the hydrocyclone installation. Satisfactory efficiencies have been obtained with reject ratios as low as 0.5%, especially with the assistance of mitigating factors such as large density differences between the hydrocarbon and water phases or elevated temperatures to reduce the water viscosity. Although operation at the minimum reject ratio has the advantage of minimising the flow rate of the reject stream, in practice an operating margin should be provided above the minimum reject ratio. This margin assists the hydrocyclone to maintain satisfactory performance under upset conditions. A reject ratio in the order of 1.5 - 2.0% is typical.

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8.9 Disuersed hvdrocarbons - Static hvdrocvclones
m80-

Table 8.9.1 Recommended settings for reject ratio Hydrocarbon content in feed Up to 1% hydrocarbon Up to 2% hydrocarbon Recommended setting
4%

10%

8.9.3.6. Density difference
The performance of a hydrocyclone will improve with increasing density difference. Thus in principle a light condensate should be easier to separate than a heavy oil. d , rises rapidly The influence of the density difference is illustrated in Figure 8.9.6. It can be seen that , with lower density differences. The minimum recommended density difference for a hydrocyclone is in the order of 50 kg/ms, measured at operating temperatures.

20.0 17.5

~

E, 10

15.0 12.5 10.0 -

h

r .

U

7.5 .

t

I
100

50

150
Density difference (kg/rrP)

I

I
200 250

Figure 8.9.6 Variation in hydrocyclone performance with density differential

It should be remembered that characteristics of the hydrocarbons other than density difference will also
SlPM Duoilinl: Mioirrirl, EP 93-1315, RKV1.1. Niiv 1993, File r i i i r i w = XO9CYCLO.DOC

Puge 8-9-5

8.9 Dispersed hydrocarbons - Static h ydrocyclones
have an impact on the separation performance. Thus a condensate with a high density difference may be considered easy to separate, however other factors such as the resistance of the condensate to shearing forces inside the hydrocyclone or the ability of the condensate to coalescer will also have a significant effect on the overall separation performance.

8.9.3.7. Temperature / Viscosity
Variations in temperature will influence both the density difference between the phases and the viscosity of the continuous water phase. In general, higher temperatures assist separation, particularly by reducing the viscosity of the water phase. However, as discussed in Appendix F, in some cases, adverse density changes with temperature can hinder the phase separation. The influence of the water viscosity is illustrated in Figure 8.9.7. It can be seen that ,d , rises with increasing viscosity, indicating reduced performance. Thus placing the hydrocyclones in a location where the water temperature is maximised will assist in maintaining a high separation efficiency.
15.0 13.0 11.0

E,
Y

m

-0

b

9.0 7.0
5.0

0.20

0.60

1

Water viscosity (cP)

.oo

1.40

2.20

Figure 8.9.7 Variation in hydrocyclone performance with continuous phase viscosity

Temperature may have additional effects on the hydrocarbon/water emulsion, such as altering surface tension or altering emulsion stability. These effects may influence the overall hydrocyclone performance. 8.9.3.8. Pressure drop Definitions Under normal operation there are two distinct pressure drops across a hydrocyclone.

-

Where:

Pin = Feed stream pressure Pout= Water outlet stream pressure Prej = Hydrocarbon reject stream outlet

The pressure drop to the reject stream (ALP2) is the most significant as it is the greater of the two and will ultimately determine the capacity of the hydrocyclone. At an early stage in the development of hydrocyclones it was found that C, the ratio between AP2and AP, has a linear relationship with the reject ratio, as illustrated in Equation 8.9.1.

c = Pi" - Pour
Where:
C R
= constant

[

Pin - Prej

) [2)
=

is proportional to R

Eq. 8.9.1

= reject ratio

Puae 8-9-6

SIPM Driiilinh.Monurrl, EP 93-1315, Rrv 1.I , NIIV1993. File nnnre = XG9CYCLO.DOC

8.9 Dispersed hydrocarbons - Static hydrocyclones
This relationship is schematically illustrated in Figure 8.9.8.

Figure 8.9.8 Relationship between reject ratio and C

The slope of the curves in Figure 8.9.8 are characteristic for each hydrocyclone installation, but are mainly a function of the geometry of the hydrocyclone. As the pressures in and out of the hydrocyclone are easily measured, this relationship may be used as the basis for measurement and control of the reject ratio of the hydrocyclone. 8.9.3.9.

Minimum pressure drop
The minimum allowable pressure drop (inlet to reject stream) across a standard hydrocyclone is typically in the order of 4 bar. New generation hydrocyclones for low pressure drop applications have minimum pressure drops as low as 2 bar. It should be recognised that both the capacity and the turn-down characteristics of a hydrocyclone improve with increasing pressure drop. Use of a feed pump to boost the hydrocyclone feed pressure and hydrocyclone capacity may be a more cost effective solution than a greater number of lower capacity hydrocyclones operating from a low process pressure. However the feed pump must be a low shear design to avoid additional shearing of the dispersed droplets.

8.9.3.1 0. Maximum allowable pressure drop
The maximum allowable pressure drop across a hydrocyclone may be limited by a number of factors. Erosion considerations, especially if solid particles are present in the water stream. Excessive shear energy input, resulting in reduced separation efficiencies. Gas breakout in the hydrocarbon core due to the reduced pressure, interfering with the separation process. The hydrocyclone vendor should advise the maximum recommended pressure drop for a given hydrocyclone and process configuration. As a first estimate, pressure drop should be limited to a maximum of 30 bar. 8.9.3.1 1. Gas breakout The effect of gas breakout on hydrocyclone performance should be considered. As well as promoting droplet shear, high pressure drops across hydrocyclone systems can result in the formation of gas bubbles. Gas bubbles may impose additional shear forces on dispersed hydrocarbon droplets and may upset the stability of the hydrocarbon core at the centre of the cyclone. Tests at the OWTC illustrated that the performance of hydrocyclones will deteriorate if sufficient free gas is present in the hydrocyclone.

SlPM Deoilinl: Miinitiil. EP 93-1315. Rev 1.1. Nov 1993. Filr

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= XOYCYCLO.DOC

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8.9 Dispersed hydrocarbons - Static hydrocyclones
8.9.4.

InstallationKonfiguration

8.9.4.1. Process location
For systems to be operated from process pressure, the hydrocyclone should be preferably be located as close as possible to the source of the waste water, preferably upstream of level control valves to minimise shearing of hydrocarbon droplets. Hydrocyclone installations can be readily designed for high pressures (120 bar designs have been proposed for some gas production installations) and can thus can be installed immediately downstream of high pressure separators. With multiple sources of water (e.9. independent separator trains), dedicated hydrocyclone systems for each source should be given preference to a single hydrocyclone package with individual level control valves located upstream of the hydrocyclones. For pumped hydrocyclone systems low shear feed pumps must be specified. These are commonly progressive cavity pumps or specially designed low shear centrifugal pumps.

8.9.4.2. Downstream degassing vessels
If the feed stream to a hydrocyclone installation originates from an elevated pressure, a downstream degassing vessel will normally be required to remove dissolved gases from the deoiled water stream before discharge.
The degassing vessel should be designed to allow oil skimming from the surface. Careful design of the degassing vessel can utilise the generated gas bubbles to create a flotation effect in the vessel which can assist in the removal of the finely dispersed hydrocarbon droplets remaining in the water stream. At the time of writing, one hydrocyclone vendor has applied to patent the use of a skimming vessel downstream of a hydrocyclone package however the validity of this patent application is under investigation. Experience indicates that a carefully designed degassing vessel can achieve further reductions in the effluent hydrocarbon concentration in the order of 10-15%. This reduction is sometimes supported by upstream chemical addition to assist in the coalescence, flocculation or flotation of hydrocarbon droplets in the skimming vessel. The degassing vessel is normally designed with a nominal residence time of 2 minutes to allow for degassing and some residence time to allow hydrocarbon droplets to rise to the surface.

8.9.4.3. Packaging
Depending on the available pressure drop the capacity of a single hydrocyclone is in the order of 4 to 20 mVh. To achieve the capacity required to process larger flow rates, individual cyclones are assembled into packages with multiple hydrocyclones in parallel. The most common packaging bundles a number of hydrocyclones into a pressure vessel with common header space for inlet and outlet streams. This modular packaging of most hydrocyclone installations has a number of distinct advantages. The capacity of the water treatment system can be upgraded by adding additional hydrocyclone packages. Thus future water treatment capacity can be phased in as required. Turn-down of the system can be accomplished by adjusting the number of hydrocyclones modules on-line. This ensures on-line hydrocyclones are operating at optimum efficiencies.

It may be possible to upgrade or replace the hydrocyclone liners whilst retaining the external pressure vessel housing.
The possibility of water escaping from the system is reduced as the number of flanges and connections is minimised and as the hydrocyclone liner is enclosed by a pressure vessel, erosion of the liner will not result in external leakage. Modular hydrocyclone packages may be dedicated to individual water sources, thus allowing level control valves to be located downstream of the hydrocyclones.

8.9.4.4. Size, Weight and Capacity
The capacity of an individual hydrocyclone is governed by the available pressure drop. Thus the total capacity of a hydrocyclone package is a function of the available pressure drop and the number of hydrocyclones in the package. Figure 8.9.13 illustrates the capacities of individual Vortoil K liner hydrocyclone packages.
Page 8-9-8
SlPM Droiling Munuid, EP 93-1315, Rev 1.1, Nov 1993, File n o m = 809CYCLO.DOC

8.9 Dispersed hydrocarbons - Static hydrocyclones
To process flows larger than that handled by a single package, a number of individual packages are combined to give the required capacity. Even when a single package is sufficient to process the total waste water flow, consideration may be given to a system comprising a number of smaller packages to allow more efficient operation during turn-down, or to be able to isolate individual hydrocyclones within the package. Similarly, individual packages for each water source allows the location of level control valves downstream of the hydrocyclone, minimising droplet shear. Figures 8.9.14 to 8.9.17 may be used to estimate the weight and space requirements of hydrocyclone packages for a given capacity and available pressure drop. The assumptions used for these estimates are included with Figure 8.9.17 and should be carefully noted. In particular, the size and weight of a hydrocyclone package is very sensitive to the training configuration. A 2 x 50% configuration was used as the basis for the estimates. 8.9.4.5.

Coalescing operation
Hydrocyclones can be configured to act as coalescence devices. For this mode of operation the reject stream is blanked off and the nominal capacity of the hydrocyclone reduced. As for a normal separation service, the hydrocarbon droplets migrate to the centre of the cyclone where they have a higher chance of coalescence. Both water and hydrocarbon streams exit from the underflow of the hydrocyclone. For more detailed information the user is referred to Section 8.3 which discusses coalescing devices.

8.9.5.
8.9.5.1.

Control configuration

Flow control
A suitable method of controlling a hydrocyclone would be to maintain a suitable ratio between the flow rates of the reject stream and the feed stream. However in practice it is difficult to obtain accurate measurements of the reject stream flow rate due to gas breakout and the difficulty in measuring two phase flow. Because of this, hydrocyclones are controlled on a basis of pressure differentials.

8.9.5.2.

Control mode Hydrocyclones have a very low residence time and will quickly establish the flow regime required to achieve separation. On this basis a hydrocyclone configuration with a single feed source will operate satisfactorily with an intermittent feed stream (such as from an on-off level control scheme). Operation with multiple on-off control sources should be avoided as the hydrocyclone installation would have to be designed for the total combined flow from all sources, but in practice, the installation would often be operating under turn-down conditions.

8.9.5.3.

Typical control configuration
Figure 8.9.9 illustrates a typical control scheme for a hydrocyclone installation. The control valve regulating the level in the upstream vessel is located downstream of the hydrocyclone to minimise shearing of the hydrocarbon droplets. Thus the rate of water discharge from the hydrocyclone is controlled by the downstream level control valve. The reject stream flow rate is controlled to maintain a constant pressure differential ratio between the feed stream and the two outlet streams. The reject stream control scheme is illustrated in more detail in Figure 8.9.10. As discussed in section 8.9.3.8, the reject ratio is proportional to the ratio of the pressure differentials. The ratio controller will regulate the overflow stream from the cyclone to maintain the desired differential pressure. This maintains a fixed ratio between the underflow stream flow rate and the reject stream flow rate Le. a fixed reject ratio. To increase the reject ratio, the setpoint for the ratio controller is simply increased.

4"I'pii
I
DP

P

Hydrocarbons

W?!%L,SP

Figure 8.9.9 Typical hydrocyclone control scheme

F k ; ;
Ralm

- - - _ - - - - - - - r - - - - -

*PI

Setpoint

j

;AP,

,

+*I-:
I

c+--

1

As an example consider the control action if the level in the
further, increasing the flow rate through the hydrocyclone.
SIPM Denilinji Miii~uril.EP 93-1315. Rev I I , Ncrv 1993. File t i i i t i ~ e = XG9CYCLO.DOC

Hydrocarbons

Water

*

H7W17P

Hydrocyclone r&ect ratio control scheme

Puge 8-9-9

8.9 Dispersed hydrocarbons - Static hydrocyclones
Due to the higher flow, the pressure drop across the hydrocyclone will increase, resulting in a decrease in the water outlet pressure (Pout)and a drop in AP,. The calculated value of C will increase, thus to retum C to setpoint the ratio controller will open the reject stream control valve. This will lower the reject stream outlet pressure (Prei), hence lowering AP2 and reducing the value of C back to setpoint.

8.9.5.4. Multiple feed control configuration
Figure 8.9.1 1 illustrates a control scheme for a multiple feed hydrocarbon installation. A backpressure controller is used to maintain a set pressure downstream of the level control valves and upstream of the hydrocyclone. The level control on each vessel can operate independently against the set backpressure, while the backpressure itself is regulated by the hydrocyclone water discharge control valve.

,
Hydrocarbons Water

The control of the overflow and reject ratio can be Figure 8.9.11 performed using the pressure differential ratio Control Multiple feed hydrocyclone control scheme discussed in the previous section. For clarity the differential pressure transmitters have not been illustrated in Figure 8.9.4.

mwMP

Although in some cases the use of a common hydrocyclone is required, the use of individual hydrocyclone packages with control valves located downstream of the hydrocyclones is generally preferred. This maximises the droplet size in the feed to the hydrocyclone and will thus improve the hydrocarbon removal efficiency.

8.9.5.5. Pumped feed configuration
Figure 8.9.12 illustrates a control scheme for a hydrocyclone installation utilising a feed pump. The feed pump may be either a positive displacement pump (e.g. progressive cavity pump) or a centrifugal pump designed for low shear operation. This scheme was used on the Kittiwake installation using a positive displacement pump.

; " I * ,
m F J
Fc

If there is spare capacity available in the upstream vessel, the recycle stream may be recycled back to the inlet of the water source vessel. This has the advantage of allowing additional residence time for the small recycled hydrocarbon droplets to coalesce.
Positive disolacement pumps

Hydrocarbons

Water

Figure 8.9.12 Hydrocyclone control scheme with pumped feed

Positive displacement pumps are normally progressive cavity pumps (e.g. Moyno) which have low shear characteristics. The pump speed should be set to pump at a rate slightly higher than the maximum water rate expected from the water source. This will ensure that the system always operates with some recycle and can absorb any higher than normal water rates without regularly adjusting the speed of the pump. A 10% recycle is typical. The combination of the positive displacement pump and the recycling water stream will maintain a set flow through the hydrocyclone, even under turn-down conditions. This ensures that the flow through the hydrocyclone is always sufficient to ensure a high separation efficiency. Centrifuaal pumos Provided they are designed for low shear operation, centrifugal pumps may also be used for hydrocyclone feed pumps. Vortoil suggest the following criteria for centrifugal pumps to minimise shear forces in the pump; Slow speed e.g. a four pole motor speed (ca. 1800 rpm 6 3 60Hz) High pump efficiency, preferably > 70% Large discharge nozzle (velocity preferably less than 5.5 m/s) High specific speed, preferably N , > 700 Closed impeller design (to minimise slippage)

0

0

Poge 8-9-10

SlPM Deoiliny: Mmuol, EP 93-1315. Rev 1.1. Nov 1993, File name = XG9CYCLO.DOC

8.9 Dispersed hydrocarbons - Static hydrocyclones
Trial work on the shear characteristics of different pump designs is discussed in reference Ref.2.05.1 .j.

8.9.6.

Operational considerations

8.9.6.1.

Blockage of the reject stream exit port
The size of the hydrocarbon reject stream exit port is generally quite small, in the order of a few millimetres. Any foreign material which enters the hydrocyclone with a density lower than that of water will migrate to the centre of the hydrocyclone and may block the reject stream exit port. The effects of such blockage can be minimised through the use of strainers and/or a backwash system. Strainers can be specified upstream of the hydrocyclone package to remove foreign materials before they enter the hydrocyclone. Such strainers are particularly useful during start-up and commissioning. However, there is a possibility that strainers may induce additional shearing of the hydrocarbon droplets. As such strainers should selected on the basis of having a relatively coarse aperture size (in the order of 300pm) and minimum pressure drop.

A backwashing system should be specified on the reject oil stream. The backwashing system uses a stream of water or gas to reverse the flow in the reject stream and remove any material blocking the exit port. The underflow from another hydrocyclone may be used for backwashing.
The reject stream should be blocked in downstream of the backflushing point to ensure the full flow of the backwashing is directed into through the reject port of the hydrocyclone and that any foreign material is carried out though the underflow of the hydrocyclone. Due to the short residence time in the hydrocyclone backflushing is only required for a short period e.g. 15 seconds.

8.9.6.2. Effect of solids
As sand has a density higher than water it will migrate to the walls of the hydrocyclone and exit with the water stream. Small quantities of sand should not have a direct impact on the performance of the hydrocyclone, however the sand may have a number of indirect effects such as: Erosion of the liners. Potential accumulation of solids in the outer vessel shell of a hydrocyclone packaged module. In some cases, solids may also potentially block the relatively small hydrocarbon reject port. Fine solids may stabilise a smaller hydrocarbon droplet, reducing the performance of the hydrocyclone. Hydrocarbons adhering to the solids will contribute to the hydrocarbons exiting with the water stream. The allowable sand content in the feed to a hydrocyclone will be dependent on a number of variables that have a bearing on erosion such as the fluid velocity in the cyclone (pressure drop), the materials of construction, the hardness of the sand etc. As such it is not possible to simply define a limit on sand content. Some erosion of liners has been experienced for the Shell Expro North Cormorant hydrocyclones. The Shell Expro Eider installation uses upstream sand cyclones to reduce the solids loading on the deoiling hydrocyclones. An alternative under consideration for the Maui A gas platform (New Zealand) is the use of erosion resistant materials for the hydrocyclone liners such as the use of boron diffused inconel or Stellite inlet sections combined with stainless steel reducing sections. When hydrocyclones are bundled together in pressure vessels with a common head collecting the water discharge, provision should be made for removal of any sand that may collect in the head. In severe cases, sand will need to be removed upstream of the hydrocyclone system to avoid problems with blockages or erosion. In this situation consideration should be given to a sand removal system that can also assist in the coalescence and removal of hydrocarbon droplets.

8.9.6.3.

Operating experience
Hydrocyclones are considered a well established technology with numerous installations throughout the world. Table 8.9.2 summarises the operating performance of hydrocyclones in a range of Shell installations and trials.

SlPM DmilinK Mimacil. EP 93-1315. Rev 1.1. Nov 1993, File nciinc = Xo9CYCLO.DOC

Puxe R-9-ll

8.9 Dispersed hydrocarbons - Static hydrocyclones

lo00

100

10

1
1 10

100

Pressure drop (bar) Figure 8.9.13 Variation in hydrocyclone capacity with available pressure drop Based on Vortoil K liner packaged modules (Jan 1993)

16.0
14.0 * 0

?
I

h

12.0
10.0

v)

a t ,

5

5

0.0

0

100

200

--

300

400

500 Capacity (mVh)

600

700 dp 15 bar

800

900

1000

dp5bar

-dplObar

- -x- -

Figure 8.9.14 Operating weight of hydrocyclone package (Low pressure drop applications) (See assumptions after Figure 8.9.17)

Page 8-9-12

SIPM Deoilinx Monutrl, EP 93-1315 Rev 1.1. Nov 1993. File nume = XWCYCL0.DOC

8.9 Dispersed hydrocarbons - Static hydrocyclones

25.0

a
C ( I ) C
v)

20.0

Y

.-

B 15.0 E m
c

.z 10.0

8

3

Y

5.0
0.0

0

200

-

400
dp 20 bar

600

Capacity (mVh)

800

lo00

1200

1400

dp 25 bar

-

-X-

-

dp 30 bar

Figure 8.9.16 Operating weight of hydrocyclone package (High pressure drop applications) (See assumptions after Figure 8.9.17)

9.0

E 7.0
a
Y

8.0

a m ,

6.0

25 . 0

.- 2.0
L

. E3.0
u l

Y

1.0

0.0

0

100

200

300

400

500 600 Capacity (mVh)

700
dp 15 bar

800

900

lo00

--* dp5bar

-dplObar

-

-XI

Figure 8.9.16 Footprint area of hydrocyclone package (Low pressure drop applications) (See assumptions after Figure 8.9.17)

~

SlPM Deoihnl: Mmwnl. EP 93-1312, Rev 1.1, Nnv 1993. Fde nome = XO9CYCLO DOC

Page 8-9-13

8.9 Dispersed hydrocarbons - Static hydrocyclones

10.0 9.0

.&
v

m 6.0 2 m E 5.0 = I ' 4
L

E

7.0

8

4.0

1.0

0.0

0

200

-

- 400
600

800

1000

1200

1400

Capacity (m3/h) dp 25 bar

dp 20 bar

-

OX-

dp 30 bar

Figure 8.9.17 Footprint area of hydrocyclone package (High pressure drop applications)

AssumDtions for hvdrocvclone weiahts and footmint areas in Fiaures 8.9.14 to 8.9.17 1. 2. 3. Equipment sizes are based on Vortoil K liner packages Weights and sizes are for skid mounted packages inclusive of typical piping, valves, structural steel etc. Each skid contains 2 standard Vortoil K liner vessels with the maximum number of liners per vessel. Each vessel is sized for 50% of the required flow, thus a single skid represents a 2 x 50% package for the given flow rate.

Puge 8-9-14

SIPM Droiling M ~ n u t r l EP . 93-1315, Rrv 1.1, Nriv 1993, File name = 809CYCLO.DOC

Field trial or Installed Date Inlet Outlet Hydrocarbon Solids handling Use of equipment hydrocarbon concentration chemicals removal (date of equipment Installation efficiency concantratlon (mg/l) In brackets) (rngn) New Zealand. Maui A Vortoil K liners Field tests 1992 14 to 20,000+ 2 to 42 mgil 70 lo 99% Not known None used platform mg/l Typically 19 mg4
Oman. Onshore Marmul, Rima and Lekhwair oil fields

Location

Equipment

Comments

Reference

Trial units TR12 (vendor not known) and FEU-301 (Vortoil).

Field trials. Marmul (M) trials in normal typeface. rn underli n 4 and Lekhwair (L) trials are in italic.

1991 (M)400t02MM Average 1198

AwaQEm(L) 8 lo 13

BlMW.44

(M)175101060 Average 642 IRI 15 to 49 (L) 5 to 8

'MI Averaoe 46%INot known
I ,
I

I

I

RI A v e a rQ e Z -B i

(L)Average 44%
berage 48% Not known

Inlet concentrationvaned over wide range, outlet concentrationsg o d . Operates with a very high inlet oressure 1120 to 150 bar) with a oressure dra ]in the order of b0 bar. IChemicals found Ilnvestioations included measurement of drODlet to have a small size distributions.Cyclone efficiency was benefit. but not consideredto be poor due to very small droplet optimised. sizes in feed stream. Performance from the cyclone was relatively poor. Ignoring spurious results gives a typical efficiency of 65%. The high efficiencycyclone gave a higher efficiencyin the order of 70 to 75% and more consistent performance. The degassing vessel tended to lower the effluent oil level by a further 10% Not used KSLA investigation into droplet size distributionsat inlet and outlet of hydrocyclones. Determinedcut off diameler to be in the order of 10 to 15 pm. Not used Performance considered to be very good, especially when inlet hydrocarbon concentrations are very high. Not used, Upstreamuse of corrosion inhibitors results in a however see much higher concentration reponing lo the comments hydrocyclones, presumably due to a smaller regarding use of droplet size. However efficiency of cyclone was the CI same with or without CI. The K liner is more etficient than the 35 mm design. Flocculation agent recommended. Demulsifiers and corrosion inhibit. resulted in lower performance. Not used Various chemicals tried, none etfectivein trials

S.2.j

.5.2.f

52.e

UK, North Sea. North Vortoil(4 in 1 Detailed trials on an existing Cormorant platform design) installation, including KSLA droplet size analysis. Norway, Nonh Sea, Vortoil Installed equipment Murchison platform Norway,Troll west gas province Vortoil Trials conducted during production tests. Compared 35 mm cyclone and K liner. Also contrasted the performancewith and without corrosion inhibitor (CI). K liner results in italics (K). Equipment trials conducted during production tests Without CI 28
~

M to 95%
5 8 to 100% rypically 76%

Not known Not known
Not known

.5.2.h and S.2.i .5.2.d ,529

35 mm 90% Yliner-94%

-

Without CI - 268

(K)W#b CI - 40 (K)Wffhouf Cl -

Norway, Troll oil field Not stated

3 7 to 95%

Not known

Droplet size from oil separator measured as 65% .5.2.c smaller than 10 pm. Hydrocyclone performance alone was not good enough. However, it is proposedthat Chitosan be used to flocculate the oi droplets to improve the hydrocycloneperformance. Generallygood performance. Some sand blockageswhen upstream desanding cyclones are 993 deoiling uestionnaire

UK. North Sea, Eider Vortoil platform

Installed equipment (1992)

Typically

Typically 16mgl

3 0 %

Sand cyclones used upstream.

SIPM Deoiling Munuul. EP 93-1315. Rrv I . I . Nov 1993. File numt = TAB8-9.1

)C

Table 8.9.2 Page 1 of 2 Deoiling equipment summary table Hydrocyclones

-

-

Location

Equipment

UK, North Sea, Kittiwakeplaltorm

Vortoil

Field trial or Installed Date Inlet Outiet Hydrocarbon Solids handling Use of hydrocarbon concentration removal chemicals equipment (date of equipment Installation concentretion (mgrl) efficiency in brackets) (mgh) Not known Not used Commissioningtrials of installed 1993 Typically 40 mgl Typically 9 mgn Not given equipment (1992)
8 to 10 mgl 1993 Not known Est. Bo - 5OOrngl

Comments

Reference

UK, North Sea, North Vortoil(4 in 1 Installed equipment (1987 to Cormorant platform design) 1989) UK, North Sea, Vortoil Fulmar Alpha platform Norway, Draugen Merpro platform Montassa Hydropak OWTC BWN Vortoil Installed equipment (1992) Installed equipment (1993) Equipment testing centre

Est. 90%

Sand results in some erosion. Not known

Not used

1993 est.50-150mql 12to15mgll 1993

Nolgiven

Not used

Results are from limited commissioningtests. Water production rates are currently too low for hydrocyclone operation. Normal performancegood. Some problems experienced with blockage of reject ports due to upstream HzS scavenger/demulsifier chemical trials. Recently installed (1992). Performance good. Platform to be commissioned October 1993

1993 deoiling questionnaire 1993 deoiling questionnaire 1993 deoiling questionnaire t 993 deoiling questionnaire

-----

____.

_____

_____

...__
Scale inhibitor, demulsifier had no effect. Corrosion inhibitor reduced efficiency

1990 Tested from 50 to 1888 mgA

Ranged from 15 Ranged from 50 Tested with 200 to 437 mgn to 82% mgn of 300pm Average 77% sand. No effect on performance.

OWTC

CO~OM, Vortoil EauiDment testina centre

1990 Tested at 200, 8 20pm droplets 8 20pm droplets Not tested 400 and 6M) m@ c 40 rngl Efficiency 92%
8 W m droplets B 10pm droplets 40 to 120 m@ Elliciency 80%

-

Hydroswirl (MPE), Krebs and Hydropak OWTC lvortoil F, G
I

I

lEauiDment testina centre

1992 Tested from 50 Results from 15 Efficiency ranged Not tested 110 2200 mg4 110 180 mgl. lfrom wer 90% I for 30pm Vortoil and Krebs droplets down to gave best 70% for lOpm performance droplets 1993 Tested from 55 Results from 7 to Efficiency ranged Not tesled to968mgl 65mgll from 79 to 95%

SIPM Drrriling Munuol. EP 93-1315. Rev 1.1. Nov 1993. Fite nume = TABX-9.1

I

I

EP 90-2641 First series of OWTC trials comparing performance of a static hydrocyclone, rotary hydrocyclone and flotation unit: Variables tested includedflow rate, reject ratio, hydrocarbon concentration, droplet size, effect of chemicals, gas injection, water temperature and salinity. hydrocarbon density and effect of solids. EP 90-3599 Corrosion Second set of OWTC trials comparing inhibitor performance of a static hydrocyclone. rotary appeared to aid hydrocyclone and centriluge for separation of droplet condensate. Variables tested included flow rate. coalescence and hydrocarbon concentration, temperature. salinity. improved droplet size and effect of corrosion inhibitor. performance Not tested Third trial at O W C compared lour "New EP 92-1900 I Igeneration"hydrocyclones. Variables tested I included oil type, concentration. droplet size. water temperature and salinity, flow rate and reject ratio. Empiricalmodels were developed to allow the performance of the hydrocyclones to be predicted. EP 93-1492 Fourth trial at OWTC comparing new G and K Not tested liners against older F liner designs. Found no significant difference for large oil droplet sizes and concentrations, however K liner does perform significantlybetter for small droplet sizes and at low pressure drops.

Table 8.9.2 Page 2 of 2 Deolling equipment summary table Hydrocyclones

-

-

8.10 Dispersed hydrocarbons - Rotary hydrocyclone
8.10. 8.10.1. ROTARY HYDROCYCLONE Introduction
Hydrocyclones enhance phase separation by generating a circular motion of the fluids to be separated. However, while a static hydrocyclone generates fluid rotation using the pressure drop of fluid itself and the geometry of the cyclone, the rotary hydrocyclone generates fluid rotation by spinning the inner cyclone walls. A rotary hydrocyclone design is illustrated schematically in Figure 8.10.1. The design and performance of a rotary hydrocyclone tends to fall between the static hydrocyclone and the centrifuge. The inner shell of the hydrocyclone is mechanically rotated using a belt drive system. The spinning of the shell and the impeller at the top of the shell impart the required rotation to the oily water. The hydrocarbon droplets migrate to the centre of the rotary hydrocyclone, forming a thin core of the hydrocarbon phase. Unlike the static hydrocyclone, the hydrocarbon core does not flow in a reverse direction, but leaves the rotary hydrocyclone through a reject needle at the same end of the cyclone as the water exit. The major advantage of the rotary hydrocyclone over the static hydrocyclone is that generating the fluid rotation using a rotating shell results in a more stable flow profile within the cyclone with less internal turbulence. This minimises shearing of the hydrocarbon droplets and results in an improved separation performance, a more stable operation and a wider operating range than a static hydrocyclone. The major disadvantage is a more complicated mechanical system involving rotating parts, seals and the attendant operation and maintenance considerations. As there are only a few installations using rotary hydrocyclones (none within Shell), there is relatively little information available indicating long term performance and reliability characteristics.
Oily water in

Mechanical seals Supporting bearings

8.10.2.

Definitions
The following definitions are commonly used for rotary as well as static hydrocyclones. Feed: Underflow: Reject stream: Reject ratio (R): The oily water feed stream entering the hydrocyclone

Figure 8.10.1 Rotary hydrocyclone

The clean water stream exiting from the tail of the hydrocyclone The concentrated hydrocarbon stream exiting the cyclone though the reject needle. The ratio of the reject and feed stream volumetric flow rates;

8.10.3.

Performance variables
The flow patterns and forces acting within a rotary hydrocyclone are complex and unlike traditional gravity based separation equipment cannot be simply described in terms of Stokes law. However, in general terms, the variables present in Stokes law will have an strong influence on the separation performance of the hydrocyclone and these variables are examined in the following discussions.
A number of graphs are presented illustrating the influence of some of the more important variables on separation performance. Where possible these results have been contrasted against the performance of

SlPM Driiilinx

Miiiiuiil.

EP 93-1.ZlS. Rrv 1. I .

Niiu

1993. File iiiiiiie = XIODYNAM.DOC

Puxe 8-10-1

8.I O Dispersed hydrocarbons - Rotary hydrocyclone
the static hydrocyclone. Although these figures have been based on actual equipment trials, they are for illustrative purposes only and should not be used in isolation to predict the potential performance of a hydrocyclone installation. The actual performance of a particular hydrocyclone installation will be dependent on the net effect of all performance variables, particularly the size distribution of the hydrocarbons in the feed to the hydrocyclone.

8.10.3.1. Hydrocarbon droplet size
From Stokes law (Appendix F) it is known that diameter is the dominant variable affecting the buoyancy of a hydrocarbon droplet. Although Stokes law cannot be directly applied to a rotary hydrocyclone, the droplet size will have a similar effect on the buoyant forces which cause the hydrocarbon droplet to migrate to the centre of the hydrocyclone. Thus, as the size of a hydrocarbon droplet increases, the rising velocity of the droplet increases and the droplet has a higher probability of migrating to the reject oil stream before leaving the hydrocyclone. Similarly, as the droplet size decreases, there will be a reduced probability that the droplet will migrate to the reject oil stream, and an increased probability of the hydrocarbon droplet exiting with the water stream. Figure 8.1 0.2 illustrates the effect of droplet diameter on the reduced migration probability (the reduced migration probability simply being a means of expressing the probability that a hydrocarbon droplet will be removed from the water stream, see Appendix I). From this figure it can be seen that; The probability of a droplet being separated increases with increasing droplet size Up to the order of 60 pm, the rotary hydrocyclone has a better chance of separating a given droplet size than a static hydrocyclone. The cut-off diameter for the rotary hydrocyclone is in the order of 8-10 pm and is more sharply defined than that of the static hydrocyclone.
1101

-

0

10

20

-

30

40

50

Medium droplet diameter (pm)

60

70

80

90

100
W6117W

Rotary hydrocyclone

-..*.... Static hydrocyclone

Figure 8.10.2 Hydrocarbon droplet removal probability versus droplet diameter

Given the significance of droplet size on the separation performance it is important to maximise the droplet size reaching the hydrocyclone by avoiding shearing and promoting coalescence wherever possible. Hydrocyclones should be located as close as possible to the source of the oily water, preferably upstream of control valves. For pumped hydrocyclone installations, the feed pumps should be a low shear design.

8.10.3.2. Flow rate
Figure 8.1 0.3 illustrates the variation of the separation efficiency of the rotary hydrocyclone with flow

Puge 8-10-2

SIPM Deoilinh.Mcrriucrl, EP 93-1315, Rrv 1.1. N m 1993, File ncrmr = XIODYNAM.DOC

8.10 Dispersed hydrocarbons - Rotary hydrocyclone
rate. As the rotation of the liquid within the cyclone is generated by the rotation of the cyclone body, the centrifugal forces generated will not fall with lower flow rates. Thus it can be seen that high separation efficiencies are maintained over a wide range of flow rates, and that separation performance improves at lower flow rates. This is in contrast to the static hydrocyclone where the centrifugal forces are generated by the flow rate and velocity of the fluid itself. From Figure 8.10.3 it can be seen that the separation efficiency for the static hydrocyclone is strongly dependant on flow rate with the separation performance deteriorating dramatically under turndown.

20
10

0

..x..
0
50

I*
8.10.3.3. Rotation speed

100 150 Percentage of nominal flow rate (%)

Rotary 1685 rprn

-

Figure 8.10.3 Hydrocarbon removal efficiency versus flow rate and rotation speed

--

200

250

1

Rotary 2250 rpm

..-*.... Static hydrocyclone

I

W511703P

The speed of rotation of the rotary cyclone can be adjusted by controlling the speed of the driving motor. Figure 8.10.3 illustrates the effect of rotation speed changes on the separation efficiency of the hydrocyclone. It can be seen that as the speed of rotation increases, the separation efficiency increases due to the greater centrifugal forces being experienced within the cyclone. The rotation speed will also impact on the pressure drop and flow capacity of the cyclone. The higher the rotational speed, the higher the pressure drop across the cyclone, hence the lower the capacity. 8.10.3.4. Inlet hydrocarbon concentration

As with the static hydrocyclone, the rotary hydrocyclone will maintain a high efficiency in the presence of high inlet hydrocarbon concentrations. However, it must be recognised that the hydrocarbon removal efficiency is simply a ratio between the inlet and outlet hydrocarbon concentrations. Thus as the inlet concentration rises, the outlet concentration will also rise.
8.1 0.3.5. Pressure drop The geometry of the rotary hydrocyclone does not present the same type of flow restriction as a static hydrocyclone. The controlling aspect of the pressure drop across the rotary cyclone is not the geometry of the cyclone or the flow rate through the cyclone, but the losses induced by the rotation forces imposed on the liquid. Thus, although the pressure drop across the rotary hydrocyclone will increase with flow rate, this increase is not as dramatic as that for the static hydrocyclone. This behaviour is illustrated in Figures 8.10.4. and 8.10.5, showing the pressure drops to the product and reject streams respectively.

As expected, it can be seen that the pressure drop across the rotary hydrocyclone is more dependent on the rotation speed of the cyclone than on the flow rate through the cyclone. In contrast, above the design
SIPM Deoilinji Monuol, EP 93-1315. Rev 1.1, Nov 1993, File iiwne = XIODYNAM.DOC

Puge 8-10-3

8.10 Dispersed hydrocarbons - Rotary hydrocyclone
throughput the pressure drop across the static hydrocyclone increases exponentially.

As with the static hydrocyclone, it can also be seen that the pressure drop to the rotary hydrocyclone reject hydrocarbon stream is always higher than the pressure drop to the effluent water stream.

1

Percentage of nominal feed rate (%)
--.b--- Rotary 2250 rpm

-

Figure 8.10.4 Pressure drop from the feed stream to the product stream for static and rotary hydrocyclones

-

- Rotary 2815 rpm

....*....Static hydrocyclone

I

H76117IDIP

16
14

.

.... . ..... .

,,

. . .,

..

.

.

.. . . ..... .. ...

.. .

.. . .. . .

..

:y’

12
10

. 0”’

0

6
4

2
0

0

50

100 150 Percentage of nominal feed rate (“A)

200

250
mii7mw

*Rotary 2250 rpm

-

L F

- Rotary 2815 rpm

...-*.... Static hydrocyclone

Figure 8.10.5 Pressure drop from the feed stream to the reiect stream for static and rotary hydrocyclones

8.10.3.6. Reject stream ratio
The optimum reject ratio for the rotary hydrocyclone is fixed according to the rotation speed of the cyclone and the size of the reject needle. It is usually set at a discharge rate of 0.5 litres/h/rpm, though different needle sizes will have different discharge rates.

P q e 8-10-4

SIPM Droilinji Monuol. EP 93-1315, Rev 1.1, NIJV1993, File name = XIODYNAM.DOC

8.I O Dispersed hydrocarbons - Rotary hydrocyclone
8.1 0.3.7. Density, viscosity and suspended solids As with static hydrocyclones, the performance of the rotary hydrocyclone will improve with increasing density difference between the hydrocarbon and water phase, and with decreasing water phase viscosity. During trials at the OWTC suspended solids were found to have a more significant impact on the rotary cyclone than the static cyclone. This was suspected to be due to the accumulation of solids on the wall of the rotary cyclone at the water outlet end, upsetting the flow pattern within the cyclone. Thus accumulation As with the static cyclone, excessive levels of solids in the hydrocarbon phase may result in blockage of the oil reject port. If significant quantities of suspended solids are expected in the feed it is recommended that the solids are removed through a upstream separation stage. Small quantities of solids can be handled provided they do not block either the water or hydrocarbon exit port. As the wall of the cyclone is rotating at a similar speed as the fluid, erosion due to the presence of solids should not be a problem.

8.10.4.

Installation/Configuration

8.10.4.1. Process location For systems to be operated from process pressure, the rotary hydrocyclone should preferably be located as close as possible to the source of the waste water, preferably upstream of level control valves to minimise shearing of hydrocarbon droplets. With multiple sources of water (e.9. independent separator trains), dedicated hydrocyclone systems for each source should be given preference to a single hydrocyclone package with individual level control valves located upstream of the hydrocyclones. The process location must consider the mechanical design limits of the cyclone. The design pressure is 20 barg with a maximum operating temperature of 110°C. For pumped hydrocyclone systems low shear feed pumps must be specified. These are commonly progressive cavity style pumps or specially designed low shear centrifugal pumps. 8.1 0.4.2. Downstream degassing vessels If the feed stream to a hydrocyclone installation is from an elevated pressure, a downstream degassing vessel will normally be required to remove dissolved gases from the deoiled water stream before discharge. Careful design of the degassing vessel can utilise the generated gas bubbles to create a flotation effect in the vessel which can assist in the removal of the finely dispersed hydrocarbon droplets remaining in the water stream. Thus the degassing vessel should be designed to allow oil skimming from the surface. At the time of writing, one hydrocyclone vendor has applied to patent the use of a skimming vessel downstream of a hydrocyclone package however the validity of this patent application is under investigation. Experience indicates that a carefully designed degassing vessel can achieve further reductions in the effluent hydrocarbon concentration in the order of 10-15%. This reduction is sometimes supported by upstream polyelectrolyte addition. The degassing vessel is normally designed with a nominal residence time of 2 minutes to allow for degassing and some residence time to allow oil droplets to rise to the surface.. 8.10.4.3. Pressure drop - Definitions Under normal operation there are two distinct pressure drops across a hydrocyclone.

Where:

Pi, = Feed stream pressure Pout = Water outlet stream pressure Prej = Hydrocarbon reject stream outlet

The pressure drop to the reject stream (APJ is the most significant as it is the greater of the two and will ultimately determine the capacity of the hydrocyclone.
SIPM Deoiling Miiiiiid EP 93-1315, Rrv 1.1. Nov 1993. File
iiiiiiie

= XIODYNAM.DOC

PuRe 8-10-5

8.10 Dispersed hydrocarbons - Rotary hydrocyclone
8.10.4.4. Minimum pressure drop The minimum allowable pressure drop (inlet to reject stream) across a rotary hydrocyclone is typically in the order of 4 bar, though pressure drops as low as 2 bar can be handled. However the capacity of the rotary hydrocyclone is a function of the pressure drop though the cyclone and the rotation speed of the cyclone. Low pressure drop designs will have a lower capacity and hydrocarbon removal efficiency. Use of a feed pump to boost the hydrocyclone feed pressure and hydrocyclone capacity may be a more cost effective solution than a greater number of lower capacity hydrocyclones operating from a small differential process pressure. 8.10.4.5. Maximumepressuredrop As previously discussed, the pressure drop across a rotary hydrocyclone is a function of the cyclone geometry, the rotating speed and the flow rate. The pressure drop would be set during the design of the cyclone on the basis of the fluid characteristics and the required hydrocarbon separation performance. 8.10.4.6. Packaging Single rotary hydrocyclones are available in nominal capacities ranging from 8.3 to 132.5 mVh. However several units are normally packaged together to give the required capacity. One standby unit is normally provided in each package. 8.10.4.7. Size, Weight and Capacity

As previously discussed, the capacity of an individual rotary hydrocyclone is governed by the available pressure drop and the rotation speed of the cyclone.
Tables 8.10.1 and 8.10.2 give approximate sizes and weights for rotary hydrocyclone separation systems. These sizes have been taken from vendor brochures and should be treated as indicative only.
Table 8.10.1 Size and weight of single rotary hydrocyclones

Diameter (inches) Overall length (m) Nominal speed (rpm)
Source:

2.5

3.4

4.6

6 . 1
10

Serck Baker Dynaclean brochure. Based on a 20vm droplet size, 150 Ib pressure class.

Table 8.10.2 Size and weight of typical hydrocyclone packages, each containing six horizontally mounted cyclones.

Floor area (m2) Height (m) Operating weight (tonnes) Power requirement (kW)
Source:

27.2

Serck Baker Dynaclean brochure. It is assumed that no standby cyclone included, therefore capacity will be reduced during maintenance.

8.10.5.

Design guidelines
There are no particular design guidelines for a rotary hydrocyclone. In general the vendor is responsible for the selection and design of a rotary hydrocyclone system to suit a given process.

PURC 8-10-6

SlPM Deoiling Monunl, EP 93-1315. Rev 1.1, Niiv 1993. File nome = 8IODYNAM.DOC

8.10.6.

Control configuration

8.10.6.1. Control mode
The rotary hydrocyclone would normally be configured to operate continuously. If intermittent flow is expected the unit would typically be operated with a recycle with the recycle control valve receiving signals from the level control valves.

8.10.6.2. Typical control configuration
Figure 8.10.6 illustrates a typical control scheme for an rotary hydrocyclone installation. The control valve regulating the level in the upstream vessel is located downstream of the hydrocyclone to minimise shearing of the hydrocarbon droplets. Thus the rate of water discharge from the hydrocyclone is controlled by the downstream level control valve. The flow rate of the hydrocarbon reject stream is controlled by the flow controller on the reject stream. An alternative would be to use a positive displacement pump which will both control the flow rate and to recycie the reject stream to the appropriate location.

I

Figure 8.10.6 Typical rotary hydrocarboncontrol scheme

a
FC

-----

Water

Hydrocarbons

HIYI2mIP

8.10.7.

Operational considerations

8.10.7.1. Blockage of the reject stream exit port
The size of the hydrocarbon reject stream exit port can be relatively small, especially for the lower capacity units. Any foreign material which enters the hydrocyclone with a density lower than that of water will migrate to the centre of the hydrocyclone and may block the reject stream exit port. The effects of such blockage can be minimised through the use of strainers and/or a backwash system. Strainers can be specified upstream of the hydrocyclone package to remove foreign materials before they enter the hydrocyclone. Such strainers are particularly useful during start-up and commissioning. However, there is a possibility that strainers may induce additional shearing of the hydrocarbon droplets. As such strainers should selected on the basis of having a relatively coarse aperture size (in the order of 300pm) and minimum pressure drop.

8.10.7.2. Solids removal
As previously discussed, excessive suspended solids content has been found to reduce the hydrocarbon removal efficiency of the rotary hydrocyclone and could result in blockage of the exit ports. Where high levels of solids are expected it is recommended that they are removed upstream of the rotary hydrocyclone.

8.1 0.7.3. Operating experience
There are currently two permanent rotary hydrocyclone installations, both with Total, at the Villeperdue oil field (16 m3/h) and Bongkot, Thailand (32 m3/h). There are no known installations within the Shell group. A brief summary of the OWTC trials of the rotary hydrocyclone is included in Table 8.10.3. Additional information can be obtained by requesting the full test reports from SIPM.

SIPM Deoilinji Moiwnl. EP 9.7-13lS. Rev 1. I * No\' 199.7. File iioiiir = XIOOYNAM.OOC

PURC 8-10-7

Location

equlprnent (date of equipment Inatallatloi In brackets rotary

Inlet hydrocarbon concentration (mgn) rested from 50 to 1551 mgn

Outlet concentration
(msn)

removal efficiency

Use of chemicals Scale inhibitor, demulsitier had no effect. accumulate until Corrosion inhibitor reduced a steady state reached. efficiency

Comments

Reference

3anged from 2 I 264 mgn

EP 90-2641 First series of OWFC trials comparing performance of a static hydrocyclone, rotary hydrocyclone and flotation unit. Variables tested included flow rate. reject ratio, hydrocarbon concentration,droplet size, effect of chemicals, gas injection, water temperature and salinity, hydrocarbon density and effectof solids.

OWTC

I

Dynaclean rotary

I

Equipment testing centre

Tested al200, 400,600 and 1MM mgn

8 2Opm < 40 mgn

Efficiency 92%
B 10pm droplets Efficiency 85%

B 1Opm40 to
120mgl

-

SlPM Droiling Munuul. EP 93-1315. Rev 1.1, Nov 1993. Fi/r num = TABX-IL

I

I

Performance of rotary hydrocyclone considered good with bener and more stable performance over a wider operating range than the static hydrocyclone. Against Second set of OWTC trials comparing EP 90-3599 sxpectalions use performance of a static hydrocyclone, rotary of corrosion hydrocyclone and centrifugefor separation of inhibitor condensate from water. Variables tested included appeared to aid flow rate, hydrocarbon concentration. temperature, droplet salinity, droplet size and effect of corrosion :oalescence and inhibitor. improved performance Performanceof rotary hydrocyclone considered good, fallingbetween static hydrocyclone and centrifuge.

Table 8.10.3 Deoiling equipment summary table Rotary hydrocyclones

-

8.11 Dispersed hydrocarbons - Centrifuges
8.11.
8.11.1.
CENTRIFUGES
Introduction
The centrifuge is a separation device which uses centrifugal force to accelerate the separation of hydrocarbon, water and solid phases. Centrifuges can be used for both deoiling of water and dewatering of hydrocarbons. This manual only considers centrifuges configured for deoiling. The feed enters the centrifuge through the static A typical centrifuge design is illustrated in Figure 8.1 1.l. axial inlet pipe and is distributed through feed holes into the separator bowl. The bowl contains set of stacked discs, forming channels of less than l m m spacing. As in a plate interceptor design, the discs shorten the distance that a dispersed hydrocarbon droplet must travel before it meets an intercepting surface where accumulation and coalescence may occur.
Hydrocarbons Water

I s
Feed

Hlm6/44P

Figure 8.11.1 Typical centrifuge design

An external motor rotates the bowl and disks at high speed, exerting a centrifugal force on the rotating liquid. From Stokes Law (Appendix F), the terminal velocity of a hydrocarbon droplet being separated by density difference is proportional to the gravitational force exerted on the droplet. In a centrifuge the gravitational force is replaced by a centrifugal force which is in the order of 5000 times higher, dramatically increasing the buoyant forces on a dispersed hydrocarbon droplet. The position of the hydrocarbonlwater interface within the centrifuge is a function of the fluid viscosities, densities, throughput and back pressures. The approximate position of the interface is fixed by selecting the correct size of gravity disc when installing the centrifuge. The gravity disk is effectively a restriction orifice controlling the dense phase (water) outlet rate. Once the gravity disc is in place, the interface position can be fine tuned by varying the backpressure on either of the liquid outlet streams Solid particles collect at the periphery of the bowl. Depending on the centrifuge design and solids loading the accumulated solids can be automatically discharged or periodically removed by manual cleaning. Figure 8.1 1.1 shows the Alfa-Lava1 Leo design which discharges solids by briefly lowering the bottom half of the centrifuge bowl. This allows solids and some water to be discharged through ports in the bowl wall, to be collected in an external bowl.

8.1 1.2.

Performance variables

8.1 1.2.1. Hydrocarbon droplet size
Test work has indicated that the centrifuge can typically remove 100% of droplets down to the order of 5 pm. Manufacturers claim that hydrocarbon droplets down to the order 2pm will be removed, however this is difficult to confirm as accurate measurement of such small droplet sizes is also difficult. The actual performance for such small droplets will be strongly affected by other variables such as turbulence,
SIPM D r o i l i n ~ Monrrol, EP 93-1315. Rrv 1.1. Noli 1993, Filr

iirriiir

= XIICENTR.DOC

Puxe 8-11-1

8.1I Dispersed hydrocarbons - Centrifuges
viscosity and density difference.

8.1 1.2.2. Flow rate
The capacity of a centrifuge is effectively governed by the difficulty of the separation and residence time considerations. As flow rates increase, the residence time within the centrifuge drops, reducing the time available for separation and coalescence. For relatively easy separations a centrifuge may operate satisfactorily above the nominal capacity. However more difficult separations may experience deteriorating separation performance at throughputs above the nominal capacity.

As the flow rate of water increases, the backpressure on the water phase will increase. This will tend to shift the interface towards the centre of the centrifuge. Eventually, water will start breaking through into the hydrocarbon outlet stream.
Under turn-down conditions the centrifuge will maintain high separation efficiencies due to the increased residence time.

8.1 1.2.3. Inlet oil concentration
Centrifuges can tolerate large surges in oil concentrations. However, it must be recognised that the hydrocarbon removal efficiency is simply a ratio between the inlet and outlet hydrocarbon concentrations. Thus as the inlet concentration rises, the outlet concentration will also rise.

8.1 1.2.4. Density and viscosity
The performance of the centrifuge will improve with increasing density difference between the hydrocarbon and water phase, and with decreasing water phase viscosity.

8.1 1.2.5. Suspended solids
The disc type centrifuge is capable of handling up to 5% volume solids, in a size range of 0.5 pm to 0.5 mm. Particles greater than l m m (sand rather than sludge) should preferably be removed before the centrifuge to avoid unnecessary wear on the internals or blockage of the discs. Where high wear rates are anticipated, erosion resistant materials and replaceable erosion liners can be specified. When solids are present it is recommended that a minimum flow rate be maintained through the centrifuge to ensure solids cannot accumulate and foul the channels between the discs. The use of a centrifuge for treating drain waters is an application that may involve a relatively high solids content and extended operation under turn-down and may require a minimum flow recycle system.

8.1 1.2.6. Interface position
The position of the hydrocarbon/water interface within the centrifuge will have a significant effect on the hydrocarbon removal efficiency of the centrifuge. For deoiling operation the interface should be located towards the centre of the centrifuge, allocating more disc surface area to the water phase. The ports in the disc stack should be located to introduce feed at the approximate position of the interface. Thus the feed ports for a deoiling centrifuge will be located towards the centre of the disc stack. The position of the interface is a function of the density and viscosity of each phase, the speed of rotation, the dimensions of the centrifuge and the backpressure on each liquid phase. The position of the interface is initially established by the correct sizing of the gravity disk. The gravity disk is essentially an orifice type restriction in the clean water outlet stream, providing a suitable backpressure on the water phase to locate the interface in the desired position. Changing to a gravity disc with a smaller orifice will increase the backpressure on the water phase and shift the interface towards the centre of the centrifuge. Some fine tuning of the interface can be accomplished by adjusting the external backpressure on either liquid outlet stream. However, any significant changes in the variables that could affect interface position (e.g. changes in fluid densities over field life, change in rotation speed of centrifuge) should be corrected by changing the gravity disc.

8.1 1.3.

InstallationKonfiguration

8.1 1.3.1. Process location
Centrifuges are generally designed for low pressure operation and as such are usually the last stage in a water treatment system. The feed stream must be degassed before passing to the centrifuge.
Puge 8-11-2
SlPM Droiling Milnuid. EP 93-1315, Rev 1.1. NOV1993, File n(imr = XllCEh'TR.DOC

8.11 Dispersed hydrocarbons - Centrifuges
As with most deoiling equipment, every effort should be made to avoid shearing and to promote coalescence upstream of the centrifuge, although this is less critical for centrifuges due to their high separation efficiency for small hydrocarbon droplets.

8.1 1.3.2. Upstream degassing vessels
Excessive gas breakout in a centrifuge will upset the separation performance. As such, the feed to a centrifuge will normally be passed though an upstream degassing vessel. A vessel designed for removal of coarse solids and fitted with a plate pack to improve upstream coalescence is recommended.

8.11.3.3. Strainers
As with any rotating mechanical equipment, accidental introduction of any foreign material into the centrifuge may result in significant damage. Coarse strainers (300pm) should always be installed immediately upstream of the centrifuges to protect the centrifuge from foreign materials.

8.1 1.3.4. Pressure drop characteristics
Due to their low design pressure, centrifuges are typically fed by gravity flow or a low pressure feed pump. There is no pressure drop across a centrifuge as the design of the centrifuge ensures the discharge streams leave at a higher pressure than the feed stream. This is achieved by the use of static impellers in the discharge ports (paring discs). The blades of the impeller are immersed in the rotating liquid, converting the rotation of the liquid into a discharge pressure head. This may eliminate the requirement for separate discharge pumps, recovering some of the energy input into the centrifuge.

8.1 1.3.5. Packaging
Centrifuges are generally packaged as a unit with a suitable electric motor drive. A number of centrifuges are installed in parallel to give the required total capacity. One standby centrifuge is normally required to allow for maintenance.

8.1 1.3.6. Size, Weight and Capacity
Table 8.11.I gives approximate sizes and weights for centrifuge separation packages, based on the AlfaLava1 Leo centrifuge design. The packages are based on skid mounted units including all process and mechanical bulks.

Capacity

(m3W
13 40 100 200

Skid weight (tonnes, dry) 2.6 4.3 6.5 13.2

L
2.0 2.0 2.0 4.1

W

H
2.2 3.0 2.8 3.3

2.0 3.2 3.0 3.0

Operating Power (kw) 19 46 100 200

Configuration
1x 1x 1x 2x

5513 (1 x 100%) SS17 (1 x 100%) Leo (1 x 100%) Leo (2 x 50%)

8.1 1.3.7. Trial units
Centrifuge vendors can offer complete packaged units in a 10 foot or 20 foot container on a rental basis. These units are useful for long term field trials or as a short term solution to a water treatment problem. This circumvents the potentially high capital cost of a permanent centrifuge installation.

SlPM Deoilinl: M~inutil. EP 93-1315. Rrv ].I# Niiv 1993, File ncimr = XIICEhTR.DOC

Page 8-11-3

8.I I Dispersed hydrocarbons - Centrifuges
8.1 1.4. Control configuration

8.1 1.4.1. Typical control configuration
Once properly configured a centrifuge is essentially self regulating and does not require a complicated control scheme. Figure 8.1 1.2 illustrates a typical centrifuge installation downstream of a degassing vessel. The control valve on the water outlet stream is not used for active control, but can be used to adjust the backpressure on the water stream to alter the position of the water/hydrocarbon interface inside the centrifuge. The design backpressure conditions for the centrifuge should be known. The operating backpressure conditions can then be checked against the design backpressure conditions if the performance of the centrifuge deteriorates.

P --

- - -;

e

Hydrocarbons

Figure 8.1 1.2 Preferred hydrocarbon control scheme

HIYIWVlOP

Automatic solids removal is controlled by a timer mechanism with the discharge interval set according to the rate of solids entering with the feed stream.

8.1 1.5.

Operational considerations

8.1 1.5.1. Maintenance As rotating equipment centrifuges require regular inspections and maintenance procedures. As a guide, an Alfa-Lava1 centrifuge typically requires an 8 hour shut-down every 3 months for a mechanical inspection. A major service (24 hours) is required once per year.

8.1 1.5.2. Establishing an interface
Typical deoiling duties involve removing a relatively small quantity of hydrocarbons from a relatively large water stream. Due to the low flow rate of hydrocarbons it may be difficult for the centrifuge to develop a stable water/hydrocarbon interface. In order to develop the required interface the centrifuge may be filled with a hydrocarbon phase before start up, allowing the interface to be quickly established upon start up. 8.1 1.5.3. Backpressure As previously discussed, altering the backpressure on either of the discharge streams will affect the position of the water/hydrocarbon interface within the centrifuge with a possible impact on separation performance. Care must be taken that the backpressure on the centrifuge discharge streams is not inadvertently altered. Possible sources of backpressure changes could be modifications to discharge piping, pressure changes at the point of discharge or restrictions and blockages developing in the discharge piping.

8.1 1.5.4. Operating experience
Centrifuges are a well established technology with numerous installations throughout the world. Table 8.1 1.2 summarises the operating performance of centrifuges in a range of Shell installations and trials. Problems with disc corrosion were reported for one offshore gas/condensate centrifuge installation which resulted in a change of centrifuge vendor. Problems have been experienced by another operator with rapid build up of scale between the centrifuge discs.

Puge 8-11-4

SIPM Deoilirtc: M(tnuct1, EP 93-1315, Rev 1.1. Nriv 1993, File riame = XIICENTR.DOC

equipment (date of equipment installatioi

Brunei, Seria Terminal

I

Ana Laval

Ife5tr.

Sarawak. Labuan Crude Oil Terminal

Alfa Lava1

Performance of centrifuge was good and 2.8.2.a considered independent of droplet size and significantly better than the parallel performance of static hydrocyclone. Field trial of centrifuge for I989 110 to 1017 mgl 14 to 61 mgl Average of 95% Handled solids Chemicals used Performanceof centriluge was good, both for Ref.2.8.2.f deoiling effluent water and for without difficulty for very high inlet deoiling water and breaking emulsions. Deoiling dewateringemulsions berage 548 Concentrations performance was significantlybetter than the Average 29 mgtl existing Wemco ftotatronsystem. 1991 :I)370 lo 427 (I)160 to 210 (I) 38 to 57% 4 to 8% by Chemicals used Centrifuge considered to work significantly better 2.8.2.c dirty feed streams. Trials volume to act as than other alternatives. The use of flocculants conductedon individualstreams LlQB-kW m n t o a% llocculants made a significant difference to the perfooance. .lw=ks% i o & without chemicals (I). The level of solids is very high and i f these solids 'Me) 3 8 3 to 840 (MC) 137 to 244 (MC) 63 to 69% are coated in oil this may be contributing and mixed streams !significantly to the oil content carried out in the 1 with chemicals (MC, itatics) Long term temporary installation I993 ?Oto6000mgl 12to200mgl 60% 20 to Boo mgl Flocculant used Centrifuge consideredto work relatively well. High 1993 deoiling installed Dec 1992 rypically 150 Typically 40 to upstream soliddsludge content in feed can choke centrifuge, questionnaire decanter to be installed upstream to remove solidslsludge. Sludge may be impactingon water quality. I993 500 to 2o00 mg4 20-30 mgl Not given Not known Not known Preliminary feedback suggests excellent Not yet with very small oil droplets. performance for a very difficult water. Unfortunately referenced Water could not be cleaned by large flow rate will require many units.

Data

Inlet Outlet Hydrocarbon Solids handling Use of hydrocarbon concentration removal chemicals concentration (men) efficiency (men) I992 200 to lo00 mgl 5 to 25 mgl Not given Not known No chemicals used

Comments

Reference

-

-

-

I"

I

I

I

OFPX 413

I990 rested at 200, 0 20pm droplets Constant Not tested 1 0 0 and 600 mgl 40 mgl eliiciency of higher than 92%, B 1Opm droplets independent of 40 to 120 mgl droplet size

Corrosion inhibitor appeared to aid droplet coalescence and improved performance

Second set of OWTC trials comparing pedormance of a static hydrocyclone.rotary hydrocyclone and centrifugefor separation of condensate. Variables tested included flow rate, hydrocarbon concentration, temperature, salinity, droplet size and effect of corrosion inhibitor. Performance of centrifuge considered goad. achieving high hydrocarbon removal efficiencies even for small droplets. Dropletssize remainingin water stream was in the order of 7pm lor static cyclone, 511mfor dynamic cvclone and <2um for

EP 90-3599

I I SlPM Derrrlrng Munuuf. EP 93-131s. Rev I 1, Nov 1993, File numt = TAEX-11

oc

Table 8.1 1.2 Deoiling equipment summary table - Centrifuges

8.11 Dispersed hydrocarbons - Centrifuges

THIS PAGE HAS BEEN ALLY LEFT BLANK

Puge 8-11-6

SIPM Deoilinl: M~tnuctl. EP 93-1315, Rev 1.1, Nov 1993, File nume = XIICEhTR.DOC

8.12 Dispersed hydrocarbons - Induced gas flotation
8.12.

INDUCED GAS FLOTATION

8.12.1.

Introduction
Gas flotation is a process by which dispersed hydrocarbon droplets are removed from water by attachment to rising gas bubbles. The oily froth which forms on the surface of the water is removed by skimming or overflowing to a collection trough. Gas flotation units are generally installed as a secondary stage in a water treatment system. Inert gases, air or hydrocarbon gas are normally used for induced gas flotation. In many cases the use of air is not practical due to the need to exclude oxygen from the process (the presence of oxygen leads to concerns with corrosion, biological growth and explosion hazard aspects). Chemical additives are often used to improve the performance of the flotation process. Gas flotation units are categorised by the method used to generate the bubbles, either Induced Gas Flotation (IGF) (mechanical and hydraulic) or Dissolved Gas Flotation (DGF). Induced gas flotation is the more common in E & P operations and is discussed in this section. Dissolved gas flotation is discussed in section 8.13. Mechanicallv induced aas flotation Figure 8.12.1 illustrates the design of a single mechanically induced gas flotation cell. Rotation of the impeller draws gas down the stand-pipe where it comes into contact with the oily water. The action of the impeller forces the water and gas through the disperser which results in the formation of small gas bubbles. The bubbles rise to the surface of the water, collecting hydrocarbon droplets and forming an oily froth on the surface of the water. The froth flows over a weir into an collecting launder, often assisted by mechanically driven paddles. The clean water underflows though a port or under a baffle near the bottom of the cell.
Shaft

Upper portion of rotor Disperser breaks air into minute bubbles

Lower portion of rotor Permanent skids
HIYC*YSIP

Figure 8.12.1 Schematic diagram of a Wemco mechanically induced gas flotation cell

Hvdraulicallv induced aas flotation The operation of a hydraulically induced gas flotation cell is very similar to the mechanically induced gas flotation cell. However, instead of using an mechanically driven impeller to generate bubbles, a recirculated stream of clean water is injected into the cell through a nozzle designed to create a venturi effect. Air or gas is drawn into the cell by the venturi and dispersed as bubbles. The injected water flow also agitates the fluid in the cell. Hydraulically induced gas flotation is sometimes referred to as Induced Static Flotation (ISF).

SlPM Deoilinl: Motitrrtl. Et' 93-131.5, Rev 1.1. Nriv 1993. File tirttiie = XI2INI)UC.DOC

P q e 8-12-1

8.12 Dispersed hydrocarbons - Induced gas.flotation
Figure 8.12.2 illustrates the design of a hydraulically induced flotation cell which uses top mounted gas eductors. A typical four cell package is shown. Elbow channels are used between the cells to direct the water flow to the top of each cell and minimise short circuiting across the bottom of the cell.
Clean water from circulation pump

J

'

Input box

First flotation 'Second flotatioi Third flotation Fourth flotation Discharge box cell cell cell cell

I

I I

. I

1 Collected oil inside launder 2 Oil outlet 3 Water outlet
4 Water inlet

Figure 8.12.2 Schematic diagram of a four cell Monosep hydraulically induced gas flotation package

The advantage of the hydraulically induced design is that it replaces the mechanical driver required for each cell with a single recirculation pump that may be common for a number of cells. This can also improve reliability as a back-up recirculation pump can be provided. To capitalise on this mechanical simplicity, most hydraulically induced gas flotation designs also eliminate the mechanically driven skimming paddles by using alternative weir or level control arrangements. Hydraulically inducing the bubbles is believed to result in lower shear forces in the flotation cell and a more complete distribution of bubbles than an equivalent mechanically induced system. In theory, this should make the hydraulically induced system more effective at capturing dispersed hydrocarbon droplets and more suitable for flotation of flocculated hydrocarbon droplets. However further test work is required to validate this theory. Level probe

Striker plate

Eductor nozzle
H75117/6P

3 "

/J!=(

recirculation

Figure 8.12.3 Schematic diagram of a L'eau Claire hydraulically induced gas flotation cell

Figure 8.12.3 illustrates a cross section of an alternative design for a hydraulically induced gas flotation cell which operates in a pressure vessel. To maximise the working volume of the pressure vessel the
Puxe 8-12-2 SIPM Droilriil: Mmrictl. EP 93-1 71.5 H r v I I . N n v 1993. Filr
11li111e =

XIZINDUC DOC

8.12 Dispersed hydrocarbons - Induced gas flotation
cells use a central, top mounted froth collection trough and bottom mounted eductors.

A disadvantage of hydraulically induced flotation cells is that the recycled water stream reduces the capacity of a given cell size.
Equioment variations Two variations on conventional gas flotation systems are available from Serck Baker. The first is the use of a floating skimmer system. This is claimed to maintain a steady skimming rate regardless of the water level in the cells. This may have some benefits for floating production systems where vessel motion could upset the skimming action of conventional flotation packages. The second is the conversion of a conventional induced gas flotation package to dissolved gas flotation as first applied on the North Sea Beatrice field (ref.2.02.1 .g, 2.02.1.h). The conventional bubble inducers were stripped from the package and gas bubbles were provided by a controlled depressurisation of production water from the 1st stage separator. Claimed benefits are increased throughput and an increase from 20-60% to 70-80% hydrocarbon removal efficiency.

8.12.2.

Performance variables

8.1 2.2.1. Hydrocarbon removal efficiency The hydrocarbon removal efficiency of a single flotation cell is typically in the order of 60 to 70%. Operating experience has indicated that the packaging of four cells in series results in an overall hydrocarbon removal efficiency in the range of 70-99%. Trials at the OWTC indicated overall efficiencies of 80 to 85% with the use of chemical flotation aids. The wide variation in hydrocarbon removal efficiencies experienced in both trials and actual installations highlights the importance of field testing flotation units before selection. Bench scale flotation equipment can be used on site to test the ability of a flotation process to remove dispersed hydrocarbons and to investigate the use of chemicals to improve the flotation performance.

8.12.2.2. Hydrocarbon droplet size
Test work has indicated that the efficiency of a flotation is not significantly affected by droplet size, maintaining relatively high separation efficiencies with droplet sizes in the order of 10 microns. Experience suggests that the flotation process can remove droplets down to the order of 5pm. However, as with most deoiling equipment, performance will improve with larger droplet sizes. Thus it is important to maximise the droplet size reaching the flotation cells by avoiding shearing and promoting coalescence wherever possible. 8.12.2.3. Gas inpuUBubble size The quantity of gas entrained in the water for a mechanically induced gas flotation system is typically in the order of 8.5 m3 gas/m3 water, however most of this gas volume is simply recirculated. The quantity of external make up gas required is typically in the order of 0.05 to 0.10 m3 gas/m3 water, sufficient to maintain a gas blanket above the liquid and compensate for losses. Some operators have experienced higher gas consumption, in the order of 0.2 to 0.4 m3/m3. The actual mass flow rate of gas consumed must take into account the operating pressure of the flotation cell. Units operating at higher pressures will require higher gas mass flow rates to achieve a satisfactory bubble density in the flotation cell. When using hydrocarbon gas, the gas is often taken from the fuel gas system, through a suitable let down and overpressure protection system. Theoretical analysis of the flotation process indicates that the hydrocarbon removal performance of the flotation cell should be improved by increasing the gas bubble concentration and reducing the gas bubble diameter. The bubble size for a IGF unit is typically in the order of 100 to 400 pm. Smaller bubble sizes in the order of 40 to 70 microns are achievable in DGF systems (section 8.13). Gas bubble diameter is not easily controlled in the field. Higher water salinity and some chemical flotation aids will help support a smaller bubble size. Most importantly, the mechanism for bubble generation should be maintained in effective working order to ensure proper bubble generation. This particularly applies to blockage or erosion of the venturi systems of hydraulically induced flotation systems. Gas bubble concentration is also difficult to control in practice. Up to a point, increasing gas bubble
Puxe 8-12-3

SlPM Deoilinx Monuril, EP 93-131.5, Rev 1. I . N m 1993. File ti(itiie = XI2INI)UC.DOC

8.12 Dispersed hydrocarbons - Induced gas flotation
concentration will improve removal efficiency due to an increased probability of bubble/droplet contact. However further increases in gas concentration will eventually become counter productive by reducing liquid residence time in the cell and through coalescence of small efficient gas bubbles into larger inefficient gas bubbles. Large gas bubbles may lead to slugging of the fluids in the cell. 8.12.2.4. Inlet hydrocarbon concentration Trial work at the OWTC has indicated that the separation efficiency of a flotation unit is relatively constant over a range of 150 to 2300 mg/l of hydrocarbon in the feed stream. However, as with most deoiling equipment, even with a high hydrocarbon removal efficiency, a high inlet concentration will still result in a proportionally high outlet concentration. Very high concentrations of hydrocarbon or slugs of pure hydrocarbon are known to upset the performance of flotation units, often hindering the establishment of a froth layer. The flotation unit should be protected from such surges in hydrocarbon concentration by an upstream primary separation stage. Designing the control system of the flotation unit to maintain a overflow from the surface of the cells under all conditions will assist in the removal of any accumulated hydrocarbon layer from the water surface. 8.12.2.5. Flow rate Figure 8.12.4 illustrates the variation in efficiency of a Wemco four cell gas flotation unit with flow rate. The fall in efficiency is related to the lower residence time in each cell with increasing flow rate. The residence time in an induced gas flotation (IGF) system is in the order of four minutes, on a basis of approximately one minute per cell.
100

8 95 v
U

p
[u

m
C

90 85

$
U I”

8

75 70 65

80

60 55 50

0

10

20

30

40 50 60 70 80 90 100 110 120 130 140 Percentage of nominal feed rate (%)

Figure 8.12.4 Relationship between hydrocarbon removal efficiency and flow rate for induced gas flotation

8.12.2.6. Reject stream The froth that is skimmed from the surface of the water contains a significant quantity of water. In general, the reject stream is in the order of 1 to 3% of the total incoming water stream. Some operators have found it advantageous to operate the flotation unit with a reject stream flow rate in the order of 510% of the incoming water stream to maintain a higher skimming rate and allow the unit to quickly recover from high hydrocarbon concentrations in the inlet stream. 8.12.2.7. Chemical addition In many cases, satisfactory hydrocarbon removal performance can be obtained from gas flotation without the use of any treatment chemicals. As with all waste water treatment systems it is preferable not to use chemicals if possible as these will often be discharged with the treated effluent into the environment. However in some cases chemical addition may be required to ensure adequate deoiling performance.

~

~

Poae 8-12-4

SII’M

Deoiliiig Maiturtl.

EP 9.7-1315, Rev I 1 . N I I V1993. Filr

iwiie

= XlllNDUC DOC

8.I 2 Dispersed hydrocarbons - Induced gas flotation
Flotation aids Trial work has indicated that in some cases the performance of gas flotation may be considerably enhanced by using a suitable flotation aid. Flotation aids may act through several mechanisms such as promoting the coalescence of the dispersed hydrocarbon droplets, enhancing the attraction between the hydrocarbon droplets and the rising gas bubbles or improving bubble and froth stability. Flotation aids should be injected well upstream of the flotation cells to ensure effective mixing and to provide time for the chemical to act. General experience with flotation aids indicate that there is an optimum dosage rate. At low dosage rates performance is poor, but improves as the injection rate increases. At excessively high dosage rates the performance falls off again and the chemical can react with the froth to form a "jelly like" substance that can accumulate on the froth discharge equipment such as weirs, paddles and launders. The correct flotation aid and dosage rate can only be selected on the basis of field trials. Typical dosage rates are in the order of 5 to 50 mg/l. Other treatment chemicals The effect on flotation performance of treatment chemicals carried through from upstream operations can only be effectively investigated through field trials. However experience indicates that the presence of corrosion inhibitor can dramatically reduce the performance of a flotation unit. The mechanism for this interference is not clear, but could be either the stabilisation of very small hydrocarbon droplet sizes or interference with the attraction between gas bubbles and hydrocarbon droplets.

8.12.2.8, Suspended solids
The effect of suspended solids on the flotation performance should be carefully considered. In some cases solids can be effectively floated out of the cells with the froth, allowing the flotation cell to remove both solids and hydrocarbons. Trials in the USA have claimed 70-99% removal of solids. However in other cases poor performance of flotation systems has been experienced with waters containing high levels of suspended solids. In these cases the agitation in the flotation cell will carry some solids into the froth, but will also prevent other solids settling and these will then be carried out with the water stream. Solids may carry hydrocarbon droplets or hydrocarbon films, contaminating the effluent water. Hydraulically induced flotation systems use a recirculated water flow and venturi type induction systems to generate gas bubbles. These components may be subject to erosion if solids are present in the recirculated water stream. As flotation units are generally the second or third stage in a water treatment system, the upstream stages should preferably be designed to remove the majority of solids before the flotation stage. The flotation of some solids may be improved by the selection of suitable flotation aids. The minerals industry has a long history of separating solids using appropriate flotation aids to selectively alter the flotation characteristics of solids.

8.12.2.9. Water salinity
Some test work has indicated that the hydrocarbon removal efficiency improves as salinity increases up to approximately 3 to 4% salinity. After this point the efficiency remains constant. The mechanism of this improvement is probably related to a number of factors such as the presence of the electrolyte ions altering the surface characteristics of the bubble/droplet system, improving the attachment efficiency or altering the generated bubble size. However other test work has indicated an opposite effect, indicating a decrease in hydrocarbon removal efficiency with salinity, though this behaviour is thought to be related to the saline water interfering with the chemical flotation aids used. Through the effect is variable, it is clear that salinity will have an influence on the flotation behaviour. This is particularly important in systems which are exposed to large seasonal variations in water salinity due to rainwater ingress. It would be expected that such systems would show a seasonal variation in flotation performance.

SlPM Deoiliiip

Moiiiiol.

EP 93-1.115. Rev 1.1, N o v 199.1. Fill, i i i i i i w = XI2INI)UC.DOC

Puge 8-12-5

8.12 Dispersed hydrocarbons - Induced gas flotation
8.12.2.10. Direct gas sparging Test work, conducted by Shell Oil in 1975, indicated that higher hydrocarbon removal efficiencies than traditional induced gas systems could be obtained by direct gas sparging. Direct gas sparging has the advantage of giving the user control over the gas bubble concentration and gas bubble size, allowing the flotation efficiency to be optimised. In addition, the sparging action is more gentle than induced gas systems, improving the bubble/droplet attachment efficiency. The use of a lean sparging gas may allow the removal of dissolved hydrocarbons from the water. However, gas sparging has the disadvantage of requiring a suitable source of compressed gas for sparging, possibly requiring a small compressor to either provide a source of gas or recover sparged hydrocarbon gas.

No information is available to indicate whether further investigations have been made into direct sparged gas systems in the E & P environment.
8.12.2.11. Removal of dissolved components Although there appears to be little information available, gas flotation systems can be designed to have some stripping effect on dissolved components in the water. Monosep have been involved with a benzene stripping installation which utilises two flotation units in series. The first unit is a normal flotation cell used to remove the dispersed hydrocarbons from the water. The second unit uses lean hydrocarbon gas to remove dissolved benzene from the water stream, effectively acting as a four stage stripper. A reduction from 180ppm to 5 ppm benzene is claimed. A suitable disposal route for the stripping gas must be identified due to HSE implications.

8.12.3.

Installation/Configuration

8.12.3.1. Process location It is recommended that gas flotation units are used as a second or third stage of a water treatment system. A primary separation stage should be provided upstream, such as a plate interceptor, to provide for removal of suspended solids and slugs of hydrocarbons. 8.12.3.2. Size, Weight and Capacity Table 8.12.1 gives typical sizes of induced gas flotation packages designed for atmospheric pressure operation. The packages are free standing with an integral skid base.
Table 8.12.1 Size and weight of skidded atmospheric gas flotation packages Capacity

(m3W
1 0 68 100 250 500

Dry weight (tonnes)

Wet weight (tonnes)

(m)

L

(m)

W

H (m)

Power[l] (kW)

Power[P] (kW)

Notes: [l] Power requirements for mechanically induced gas flotation. [ 2 1 Power requirement for hvdraulically induced gas flotation. . . [3] Weights for complete skidded flotation packages.

7.9 12.3 1 8 . 1

22.0 45.0 74.2

7 . 7 9.8 11.9

2 . 6

1 . 9 2.6 2.8 3 . 3 3 . 8

6.6 10.7 21.4 3 5 . 1 67.5

2 . 2 7 . 7 11.2 24.2 33.6

8.12.3.3. Packaging A flotation cell is effectively a well mixed vessel and thus a certain fraction of the feed stream will short circuit through the cell. To achieve the required hydrocarbon removal efficiency a number of cells (typically four) are combined in series to form a single package. A discharge box is provided after the last flotation cell and is the usual location for water level control instrumentation. An input box can also be used to provide for skimming of free oil and the removal of solids, through this is usually more efficiently performed in upstream vessels. A typical four cell design is illustrated in Figure 8.12.2. Although the majority of flotation packages operate at near atmospheric pressure, designs incorporated into pressure vessels are available from some vendors. Pressurised designs may simplify some design
Puge 8-12-6
SIPM Deoiliiiji Mociucil, EP 93-1315. Rev 1.1, Nov 1993. File nome = XlZINDUC.DOC

8.I 2 Dimersed hvdrocarbons - Induced pas flotation
aspects by eliminating the need for pumps on outlet streams or the need to arrange the layout to achieve gravity flow. Some vendors market smaller flotation packages consisting of one or two cell configurations. These could be used for duties with relatively low inlet hydrocarbon concentrations, or could be used to add pre or post flotation to an existing flotation installation.

8.12.4. Design guidelines

,

Vendors are usually responsible for the sizing and design of flotation packages. As each application and associated water chemistry is different, field trials with trial units or bench scale systems are recommended to ensure that flotation will be effective and to identify the potential need for flotation aids.

8.1 2.5.

Control configurations
Due to the different equipment configurations from different suppliers it is not possible to give a standard control scheme for induced gas flotation systems. However, the following discussions highlight the operation experience obtained from controlling Wemco induced gas flotation systems which have been used in a number of Shell installations.

8.12.5.1. Conventional control A conventional basic control scheme for a flotation package is illustrated in Figure 8.12.5. The water liquid level in the flotation cells is regulated by a level controller located in the water discharge box, while the level in the froth overflow launder is controlled by an independent level controller. The water level in the cells should normally be maintained just below the top of the froth weirs, allowing only froth to flow over the weir. Variations in froth height from cell to cell can be accommodated by altering the height of the weir bars in each cell.
Hydrocaibons

Q
Water
HIt%7aOP

Figure 8.12.5 Basic flotation unit control

Although this control system will operate satisfactorily under steady conditions, it is dependent upon the generation of a stable froth layer to ensure effective removal of the hydrocarbons from the water. Loss of the froth layer will result in no hydrocarbons being removed via the overflow and all hydrocarbons must then necessarily exit with the water flow. In addition, if the level controller in the water discharge box is only configured for proportional control, upset conditions could result in an offset in the water level. An offset resulting in a low level in the cells will result in less froth overflowing the weirs and a reduction in deoiling performance. 8.12.5.2. MasterMave control system An alternative to the basic control system is the masterklave control system illustrated in Figure 8.12.6. This control scheme was successfully used on the Shell Expro Auk platform, though the flotation unit has since been decommisioned. The basic control scheme was modified by using the output from the level controller in the overflow launder (the master) as the input signal to the water level controller (the slave). The original input signal from the water level in the water discharge was disconnected. As an example of the behaviour of this system, consider the response if lack of froth overflow causes the level in the overflow launder to fall. In this event, the master controller will decrease the signal to the launder LCV to close it further to maintain level in the launder. The same decreasing output signal becomes the input to the water level controller. Perceiving the signal as a decrease in water level the water level controller will partially close the water outlet valve. This raises the water level in the cells and creates more overflow, correcting the original problem. In addition, an overflow from the flotation cells will be maintained at most times.

---+

1

2ca&ons
Figure 8.12.6 Masterlslave flotation unit control

Water

b

H7XQb7lP

The advantage of this control scheme is that it can be implemented with existing instrumentation. However it has the disadvantage in that there will be a cycling interaction between the master and slave

8.12 Dispersed hydrocarbons - Induced gas flotation
level controllers. This interaction must be minimised though careful tuning of the controllers.

8.12.5.3. Constant skimming control system
A more stable variation of the master/slave control scheme is illustrated in Figure 8.12.7.
The level in the flotation cells is still regulated by a level controller located in the water discharge box and the level in the froth overflow launder is regulated by the launder level control. However the setpoint for the water level controller is reset by a flow controller on the overflow stream. This method ensures that a constant skimming rate is maintained regardless of the feed flow rate.

I
4

I

I

]
I

Hydrocarbons

r.

Water
HI-

k

Figure 8.12.7 Constant skimmjng flotation unit control

This control scheme has the advantage in that an known overflow will be established under all circumstances. This ensures hydrocarbons on the surface of the water are constantly being skimmed from the cell, even in the absence of froth. An example of such a situation would be a large slug of hydrocarbons entering the flotation unit. Such an overload may destroy the layer of froth, resulting in no overflow into the launder. In response the overflow flow controller will raise the level in the flotation cell until the an overflow is re-established, effectively skimming the hydrocarbon from the surface of the flotation cells. The potential disadvantage of this system is that unless the setpoint of the flow controller is manually reset, the reject rate remains constant even for very low feed flow rates. In addition, it is not known whether this control scheme has been successfully implemented in the field.

8.1 2.5.4. Ratio control
A more sophisticated control scheme is the ratio control system as illustrated in Figure 8.12.8. A ratio controller is used to maintain a constant ratio between the inlet and outlet flows, ensuring only a controlled percentage of the feed flow overflows into the froth launder. To stabilise the performance of this system it is preferable to smooth the flows through the flotation unit. This can be achieved as indicated, with the setpoint for the inlet flow controller reset from the level controller of
I----------------------------

:-+I

Setpoint from upstream LCV

----:
I

I
I

,
,

I

,

#
,

I ,

,

,

IE
!

I

. . I

It

HIM26RSP

Water

k

8.12.6.1, Solids handling
As previously discussed, flotation cells should not be used for the removal of solids. The drainage system from the cells should be suitable for the discharge of any solids or sludges that do accumulate, however, in general the majority of solids should preferably be removed by upstream treatment equipment.

8.12.6.2. Chemical dosage rates
Experience has indicated that the overdosing of flotation aids can result in the formation of “jelly like” substances in the froth overflow. These can accumulate on overflow weirs, paddles and in launders. Care should be taken to avoid overdosing of chemicals, particularly during turn-down. In many situations adequate flotation performance can be achieved without the addition of chemicals.

8.12.6.3. Froth height
A characteristic of gas flotation is that the froth height is generally higher in the end cells with the lower hydrocarbon content. To some degree, froth height can be altered by changing the height of the froth overflow weirs. Further reductions in froth height can be made through controlling the gas intake rate into
8-12-8
SIPM Deoiliiiji Mniiuctl, EP 93-1315, Rev 1.1. NIIV 1993. File iwnr = Xl2INDUC.DOC

PUKE

8.12 Dispersed hydrocarbons - Induced gas flotation
the last cells, either through partial plugging of the gas intake ports or the fitting of valves to allow the gas intake rate to be manually adjusted as required.

8.12.6.4. Eductor erosion
The eductor systems for hydraulically induced flotation systems can be subject to blockage or erosion, especially if solids are present in the recirculation water. This can result in poor bubble formation and a deterioration in hydrocarbon removal performance. Eductors should be inspected during shutdowns to ensure there is not excessive wear.

8.12.6.5. Operating experience
Induced gas flotation is a well established technology with numerous installations throughout the world. Table 8.12.2 summarises the operating performance of IGF units in a range of Shell installations and trials.

SIPM Deiiiliiig Miiiiitril, EP 93-1315, Rev 1.1, Nov 1993, File i i m i e = RI2INDUC.DOC

Puge 8-12-9

Location

Equipment

A number 01 E 8 P operations

IWemco

I

USA, Midway Sunset L'eau Claire field Sarawak. Labuan Crude Oil Terminal Sarawak. Labuan Crude oil terminal Chemlink (C) Wemco (W) L'eau Claire (LC) Wemco (W)

Field trlal or insfalled equipment (date of equipment Installation I In brackets) ISummaty of the OpBrating experience with Wemco machines in a number of E 8 P locations. Pilot tests followed by lull scale installation Field trial to consider replacementsto existing Wemco system (Wemco performancein italics). Field trial to consider replacementsto existing Wemco system. (Wemco performancein ifalics).
~~

Reference

.2.2.a

.2.2.b .2.2.c

.2.2.d

USA, Shell Western. Quadricell (0) Fieldtrial to compare two IGF 1984 110 ppm for all Black Bayou, designs. Tested with and without cases Hydrocell (H) the use of chemicals (QC) (HC) Bmnei. Seria oil terminal Wemco and unspecified OAF unit. DAF uses upstream mag. and flocculation. Wemco 9 7 @ l Comparison between dissolved 1982 m gas llotation and Wernco flotation package. Wemcw results in italics (W) (W) 76 md, Operating experience with the Wemco. Laboratoryand field trials comparing Wemco and dissolved gas flotation. Wemco results in italics (W).
I
~= C TABoI-/2

UK North Sea, Auk platform USA, numerous locations

Wemco

I

SIPM Deoiling Munuul. EP 93-1315. Rev 1.1, Nov 1993. File M

.DOC

f

(ac) 20 ppm (H) 22 ppm (HC) 10 ppm 33 msn
(W) 18 m g l

(a)40 ppm

(a)64%
!x%

(ac) 82% (HC) 91%
(H) 80%

(W) 76%

.02.2.e Hydrocell found to be most reliable and best performer. Gives excellent water quality with 4 ppm of flotation aids. Based on lrials a Hydrocelldesign (HC) 4 ppm was purchased. .9.2.a 62% of solids Coagulant and Tests lound the Wemco to be more efficient at removina oil. The DGF unit has a hiaher removal llocculant. removed of solid< however it is not specified 6 the report (W) Flotation aid whether these are being remnved by a flotation or (W) 47% of sdids removed sedimentation process. Not known (QC) 8 ppm Not known Chemicals required to get suitable performance Chemicals had mixed effects (W) Chemicals did not have a significant effect Performancefound to be sensitive to chemical dosage rate and water temperature. Control system altered to improve stability. Report discusses theory. bboratory tests and lield tests in detail. Compares Wemco with dissolved gas llotation units and found Wemco to be more etticient. .2.3.a

mgll

lM)tO299mg/l 141038mg/l

90t095%

50 to 200

1510 125
(W) 10 to 50

(W) 100 to 200

20 to 83% Typically 46% (W) 62 to 94% (W) Typical&
83%

Not known

.2.1.1

Table 8.12.2 Page 1 of 2 Deoiling equipment summary table Induced Gas Flotation

- -

Location

Equipment

The Netherlands, NAM. East NetherlandsGas Fields, Drente, Twente Canada, Peace River onshore heavy oil field Canada, Virginia Hills onshore heavy oil field Canada, House Mountainonshore oil field UK, North Sea, Auk platform Brunei, terminal
Oil

Monosep

Field trial or installed Date Inlet Outlet Hydrocarbon equipment hydrocarbon concentration removal concentration (mgil) efficiency (date of equipment installation in brackets) (mgil) 25 72% Equipment trial 1992 90 mgA

Solids handling

U s e of chemicals

Comments

Reference

msn

Not known

10 mg/l flotation Trial results reported through 1993 deoiling aids questionnaire.

1993 deoiling questionnaire

Wemco US Filters Ouadricell Wemco Wemco WemCO

Installed equipment (1986) Installed equipment (1989) Installed equipment (1967) Installed equipment (1976) Installed equipment (1981)

1993 155 mgl 1993 25 mq/l

77 mgli
5 mgA

50%

Not known Not known None

80%

1993 5 to 500 mgA 0 to 100 mgA Up to 100% Typically 10 m g l Typically 0 mgl 1993

No chemicals used No chemicals used No chemicals used

._--_

.__..

._-__

__.__
No problems

____.

Secondary stage treatment, downstream of skim tank, upstream of sand filters. Secondary stage treatment, downstream of skim tank, upstream of sand filters. Typically good performance with up lo 100 mgA in feed. Etfluent oil concentration Starts to rise proportionally above 100 m@ in feed. lntemals stripped from Wemco due to 'poor performance', Cells now operates as a skim tank
only.

1993 deoiling questionnaire 1993 deoiling questionnaire 1993 deoiling questionnaire 1993 deoiling questionnaire 1993 deoiling questionnaire 1993 deoiling questionnaire Not

1993 155 to 892 m@ Typ. 380 mgA 19% 1993

15 to 100 mgl Typically 92% Typically 30 mgl
._.__

Gabon, Gamba onshore oil export terminal Thailand OWTC

L'eau Claire L'eau Claire Wemco

Installed equipment (1993) Equipment trials Equipment testing centre

------_-_

_____

____.
...__

20 to 30 ppm of Some problemswith slime and scale build up, poly-electrolyte performance varies directly with throughput at inlet to Wemco Awaiting to be commissioned

_____

.____

_____

SIPM Drnilin~ Munuul, EP 93-1315, Rev 1.1. Nuv 1993. Filenumc = TAB8-12.DOC

1990 Tested from 150 Ranged from 25 Averaged 86% Not tested to 2308 mgl to 288 mq/l lor all concentrations. Efficiency improved to 99% at end of trial with optimised flotation aid.

improvement. Corrosion inhibitor reduced performance.

only a limited nuniber of chemicalaids were tested. referenced EP 90.2641 Correct flotation First series of OWTC trials comparing aid gave large performance of a static hydrocyclone. rotary

__.__

Poor results. reason not yet known, suspect that

hydmcyclone and flotation unit. Variables tested for flotation included flow rate. oil concentration, droplet size, effect of chemicals. Very big improvement in performance when flotation aid optimised. Efficiency not atfecled by concentration increases or droplets down to 10 urn.

8.12 Dispersed hydrocarbons - Induced gasJlotation

Puxe 8-12-12

SIPM Droiliiih.Mmutrl, EP 93-1315, Rrv 1.1, NIJV1993, File ntime = X12lNDUC.DOC

8.I3 Disuersed hvdrocarbons - Dissolved aas flotation
8.1 3. 8.13.1. DISSOLVED GAS FLOTATION

Introduction
As with induced gas flotation, dissolved gas flotation assists the removal of hydrocarbon droplets by attachment to rising gas bubbles. The oily froth which forms on the surface of the water is removed by skimming or overflowing to a collection trough. Gas flotation units are generally installed as a secondary stage in a water treatment system. Inert gases, air or hydrocarbon gas are normally used for induced gas flotation. Operation with air is often referred to as Dissolved Air Flotation (DAF). In many cases the use of air is not practical due to the need to exclude oxygen from the process (the presence of oxygen leads to concerns with corrosion, biological growth and explosion hazard aspects). Chemical additives are often used to improve the performance of the flotation process. Gas flotation units are categorised by the method used to generate gas bubbles, either Induced Gas Flotation (IGF) (mechanical and hydraulic) or Dissolved Gas Flotation (DGF). Dissolved gas flotation is discussed in this section. Induced gas flotation is discussed in section 8.12. Figure 8.13.1 illustrates the design of one style of dissolved gas flotation system. Bubbles are generated by saturating a liquid stream with gas, typically at a pressure of 3 to 6 barg. As the liquid is depressurised, the gas is released as fine bubbles. The rising bubbles can attach themselves to hydrocarbon droplets and solid particles and float them to the water surface from where they can be removed.
Frothscraper Clean water launder ( 3 6 0 ' )

/

Water + flocculants

Distribution

Flocculationtank Gas saturated recyclewater

I

I

Hydrocarbons and solids Clean water Recycle water

I

Flotation gas

Saturator vessel

W

Figure 8.13.1 Dissolved gas flotation system

Recycle pump

2 4

The main advantages of the dissolved gas process over induced gas systems is the relatively gentle method of generating the gas bubbles. The absence of high shear forces in the flotation cell allows DGF to handle flocculated feed streams without breaking up the flocs. Opco trials have indicated that for unassisted water treatment an induced gas flotation system is more efficient for removal of hydrocarbons than a dissolved gas flotation system. However, the dissolved gas system has been found to be more efficient in removing fine solids. As a result, a dissolved gas flotation system would often be recommended over an induced gas system for applications requiring solids removal or where a pre-flotation flocculation stage is used or required. Figure 8.13.1 illustrates the use of an stirred vessel as the flocculation stage for the DGF system. A coagulant stage can be used before flocculation to assist the gathering of the dispersed hydrocarbon droplets into microflocs. The flocculant then gathers the microflocs into larger flocs. Coagulation and flocculation are discussed in more detail in section 8.4. Treatment chemicals can also be used to assist the removal of solids, by helping to bind the solids into the flocs, or by altering the surface chemistry to make the solids more hydrophilic and thus more likely to be gathered by the flotation bubbles. Figure 8.13.2 illustrates a common variation of dissolved gas flotation system, the use of a plate pack to
SlPM Deoilinp M(iiiuo1, EP 93-1315, Rev 1.1, Nov 1993. File iiiiiiir = XI3DISS.DOC

Puge 8-13-1

8.I3 Dispersed hydrocarbons - Dissolved gas flotation
improve the hydrocarbon separation performance.
Froth scraper /

I

I
Clean water

Hydrocarbons and solids discharge

c*TJy
Serpentine pipe

Flotation gas

-.

“------e‘-h Pipe free R e expansion gas c y cremoval i e for
Chemical injection

pump
KlYldyIlP

Figure 8.13.2 Dissolved gas flotation unit with plate interceptor and serpentine pipe flocculator

The plate pack provides a laminar flow regime which allows small hydrocarbon droplets, flocs and gas bubbles to be separated from the water stream. Also illustrated is a serpentine pipe flocculator. This type of flocculator operates in plug flow, using the natural flow turbulence and the residence time in the serpentine pipe system to promote flocculation. The stream to be saturated with gas can be the full feed stream, a proportion of the feed stream or a recycle stream from the discharge of the DGF unit. The recycle stream system is the most common, having the advantage of using a clean water stream in the saturation system (Le. no solids or hydrocarbons to contaminate the saturation equipment) and ensures that the largely hydrocarbon free recycle stream, not the feed stream, is exposed to the shear forces experienced during the depressurisation of the gas saturated stream. This is particularly important in ensuring the maximum hydrocarbon droplet or floc size enters the flotation cell.

8.13.2.

Performance variables

8.13.2.1. Typical p e r f o r m a n c e
90% or higher with a suitable flocculation stage. The use of flocculation may also assist the removal of

Field trials have indicated that a DGF unit can achieve a hydrocarbon removal efficiency in the order of

fine solids from the water stream.

If a flocculation stage is not used, an induced gas flotation system as described in section 8.12 would generally be recommended over a DGF unit.

8.13.2.2. Hydrocarbon droplet size
It is recommended that the DGF process be used in combination with an upstream flocculation system. This will gather small hydrocarbon droplets into large flocs, improving the separation efficiency. By incorporating the flocculation stage the DGF system should be relatively independent of the hydrocarbon droplet size in the feed stream.

8.13.2.3. Bubble size and concentration
The performance of gas flotation is improved by reducing the size of the bubbles and increasing the number of bubbles (bubble concentration). The typical bubble size for a DGF unit is in the order of 40 to 70 microns. This is smaller than the typical 100 to 400 vm bubble size in an induced gas flotation system. To minimise bubble size it is important to avoid any premature release of gas in the piping between the saturator and the flotation cell, and to distribute the bubbles widely into the flotation cell. This minimises bubble size by avoiding bubble contact and coalescence. Excessive bubble coalescence or a high bubble concentration will result in the formation of slugs of gas, with increased turbulence in the cell and reduced separation performance. The solubility of the gas in the water will depend on a number of factors such as the temperature of the
Puge 8-13-2
SIPM Deoilinl: Monual, EP 93-1315, Rev 1.1, NOV1993. File nume = Xl3DISS.DOC

8.I3 Dispersed hydrocarbons - Dissolved gas-flotation
water, the gas being used for saturation and the influence of impurities in the water (hydrocarbons, electrolytes, etc.). Figure 8.13.3 illustrates the equilibrium solubility of a selection of gases. It can be seen that the hydrocarbon gases are more soluble than air, and that the solubility of the gases decreases with increasing temperature.
0.10

- 70 - 60 - 50

-40 -30

-

- 20 - 15 - 10
0 . 0 1 0
10
I

Fi

20

I

30

40

I

60 Temperature “C
50

I

I

70

I

80

90

I

100

1- 0

Figure 8.13.3 Solubility of gases in water

The amount of gas released during depressurisation will be a function of the difference in gas solubility between the pressurised and depressurised water and the amount of gas that can actually dissolve into the water in the saturator. Due to the short contact time, equilibrium gas solubility will not be achieved between gas and liquid in the saturator. A saturation efficiency in the order of 70% can be expected for a simple saturation vessel, increasing to the order of 90% for a more efficient saturator using internal packings or a pump based saturator.

8 . 13.2.4. Inlet oil concentration
It is recommended that the inlet oil concentration to a DGF unit is kept lower than 500 mg/l. It is expected that as for induced gas flotation systems, very high concentrations of hydrocarbons or slugs of pure hydrocarbons would upset the performance of the DGF unit. As for induced gas flotation systems, a primary treatment stage will often be used upstream of the DGF system. The primary treatment stage should smooth the flow to the DGF and remove large hydrocarbon droplets, hydrocarbon slugs and large solid particles. As with most deoiling equipment, the hydrocarbon concentration of the effluent water will be related to the inlet hydrocarbon concentration by the hydrocarbon removal efficiency. Even with high removal efficiencies, a high inlet concentration will lead to a high outlet concentration. 8.1 3.2.5. Recycle rate The recycle rate of clean water for pressurisation is typically in the order of 10-30% of the feed rate. Increasing the recycle rate will increase the bubble concentration in the flotation cell, however at the expense of residence time in the flotation cell. 8.13.2.6. Flow rate Altering the flow rate through the flotation cell will alter the separation performance by changing the residence time. The longer the residence time, the better the performance.

It should be noted that most of the flochubble contact will often take place in the inlet piping or inlet chamber of the DGF where the bubble concentration is highest. The residence time in the inlet system is often very short, in the order of 20-30 seconds. Outside of the inlet system the bubble concentration and chances of droplethubble contact fall rapidly. Thus most of the hydrocarbonlsolids removal is accomplished in the inlet system with the bulk of the residence time in the DGF allowing for rising of the flocs and bubbles.

SIPM Deoilinl: Menuol, &P 93-1315, Rev 1.1. Nnv 1993, File nome = N13DISS.DOC

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8.I3 Dispersed hydrocarbons - Dissolved gas flotation
8.1 3.2.7. Chemical addition
Coaaulation/Flocculation As previously discussed, a DGF unit should preferably be operated with an upstream coagulation and flocculation stage to assist the separation of both hydrocarbons and solids from the water. Coagulation and flocculation is discussed further in section 8.4.
Flotation aids Trial work has indicated that in some cases the performance of gas flotation may be considerably enhanced by using a suitable flotation aid. Flotation aids may act through several mechanisms such as promoting the coalescence of the dispersed hydrocarbon droplets, enhancing the attraction between the hydrocarbon droplets and the rising gas bubbles or improving bubble and froth stability. Flotation aids should be injected well upstream of the flotation cells to ensure effective mixing and to provide time for the chemical to act. General experience with flotation aids indicate that there is an optimum dosage rate. At low dosage rates performance is poor, but improves as the injection rate increases. At excessively high dosage rates the performance falls off again and the chemical can react with the froth to form “jelly like” compounds that can accumulate in the froth discharge area. The correct flotation aid and dosage rate can only be selected on the basis of field trials. Typical dosage rates are in the order of 5 to 30 mg/l. Process chemicals The effect of oil field chemicals on flotation performance can only be effectively investigated through field trials. However experience indicates that the presence of corrosion inhibitor can dramatically reduce the performance of a flotation unit. The mechanism for this interference is not clear, but could be either the stabilisation of very small hydrocarbon droplet sizes or interference with the attraction between gas bubbles and hydrocarbon droplets.

8.1 3.2.8. Suspended solids
The effect of suspended solids on the flotation performance should be carefully considered. In some cases solids can be effectively floated out of the cells with the froth, allowing the flotation cell to remove both solids and hydrocarbons. However in other cases poor performance of flotation systems has been experienced with waters containing high levels of suspended solids. In these cases the flotation action will carry some solids into the froth, but will also prevent other solids settling and these will then be carried out with the water stream. Solids may carry hydrocarbon droplets or hydrocarbon films, contaminating the effluent water.

It is recommended that the upstream primary treatment stage is designed for the removal of the larger, rapid settling solid particles. With the correct addition of flotation chemical aids, the remaining fine solids should be able to be successfully removed by the flotation process.

8 . 1 3 . 3 .

InstallationKonfiguration

8.13.3.1. Process location
The flotation process is typically a secondary treatment process. As such it is recommended that a primary separation stage should be provided upstream, such as a plate interceptor, to provide for removal of suspended solids and slugs of hydrocarbons.

8.13.3.2. Gas saturation schemes
The DGF process requires a liquid stream to be saturated with gas under pressure which will then provide a source of flotation bubbles when the pressure is released. A number of different pressurisation schemes are illustrated in Figures 8.13.4 to 8.13.6. Full flow operation Full flow operation, illustrated in Figure 8.13.4, consists of pressurising and dissolving the flotation gas in the entire feed stream. This has the advantage of generating the maximum quantity of bubbles in the
P q e 8-13-4
SlPM Deoiliiifi M o i t u d , EP 93-1315. Rev 1.1, Nov 1993, File nctrne = XI3DISS.DOC

8.I3 Dispersed hydrocarbons - Dissolved gas flotation
flotation cell. This system has the disadvantage that the entire feed stream must be depressurised across a valve to generate the required gas bubbles afler pressurisation. Depending on the feed stream pressure, a pump may also be required to pressurise the feed stream. These pressure changes make hydrocarbon separation more difficult due to shearing of hydrocarbon droplets or the break up of flocs. Solit flow ooeration Split flow operation, illustrated in Figure 8.13.5, only pressurises part of the feed stream. This has the advantage of a smaller pressurisation pump and allows the use of a flocculation stage which will improve the flotation performance. However split flow has the disadvantage of generating less bubbles in the flotation cell and still shearing the hydrocarbon droplets and flocs in the depressurisation of the split feed stream. Recvcle ooeration Recycle operation, illustrated in Figure 8.13.6, is the most common mode of operation. Recycle operation has the advantage of minimising upstream shearing of any of the feed stream and allowing optimum flocculation. It also has the advantage of allowing more sophisticated saturator designs as the recycle water is relatively free from solids and hydrocarbons. However it has the disadvantage of a lower bubble concentration within the flotation cell as the recycle stream is only 10-30% of the feed stream. Due to the recycle, a larger flotation cell will be required for the same residence time. Feed stream from upstream process
Air Oily water

I

- -- -- - Pressure retention

Oily scum

4

Flocculating agent (if required)

I

effbent

lank

I

HIWw24P

Figure 8.13.4 Full flow operation Oily scum water

e$$$

Flocculation chamber

effluent

b

Pressure retention tank Figure 8.13.5 Split flow operation Oily scum

W75m8)2SP

,
I
I

Oily water Flocculating (if re5uired) aoent I

A

Flocculation

$&!$;

~ l . chamber

effluent ~

b

~

~

I

t, A .
Pressux retention

-w T!

I
H75m6R6P

Recycl tank ~i~ Pump

Figure 8.13.6 Recycle stream operation

One potential source of a gas saturated liquid stream is the process itself. This technique was applied on the North Sea Beatrice field in the conversion of a conventional induced gas flotation package to dissolved gas flotation (ref.2.02.1.g, 2.02.1 .h). The conventional bubble inducers were stripped from the package and gas bubbles were provided by a controlled depressurisation of production water from the 1st stage separator. Claimed benefits are increased throughput and 80% hydrocarbon removal efficiency. 8.13.3.3. Size, Weight and Capacity Due to the wide range of potential designs it is not possible to give typical sizes and weights for dissolved gas flotation equipment.

8.13.4.

Design guidelines
Vendors are usually responsible for the sizing and design of flotation packages. As there is no “standard design for dissolved gas flotation units, no specific guidelines may be given.

8.13.5.

Operational considerations

8.13.5.1. Intermittent skimming The API guide to water treatment claims one operating installation found an improvement in DGF performance by operating with intermittent skimming. This was believed to allow the formation of a stiffer, relatively stable and more concentrated foam/scum layer on the water rather than damaging the foam/scum layer with continuous skimming.

SlPM Deoilinl: Mtriiicnl, EP 9.7-1315. Rev 1. I. Niiv 199.7, Filc ililiile = X131)ISS.I~OC

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8.I3 Dispersed hydrocarbons - Dissolved Ras.flotation
8.13.5.2. Operating experience
Dissolved gas flotation is a well established technology with numerous installations throughout the world. Table 8.13.1 summarises the operating performance of DGF units in a range of Shell installations and trials.

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SIPM Droilinx M(inuri1. EP 93-1315, Rrv 1.1, Nov 1993, Filr ncime = Xl3DISS.DOC

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8.13 DisDersed hvdrocarbons - Dissolved pas flotation

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StPM Drriilinp M(iiwfi1,EP 93-1315, Rrv 1.1, NIW 1993, Filr niime = X13DISS.DOC

8.14 Dispersed hydrocarbons - Deep bed media filtration
8.14. 8.14.1. DEEP BED MEDIA FILTRATION

Introduction

8.14.1 .l. General
Deep bed media filtration involves the removal of suspended hydrocarbons and solids from waste water by passing the water through a deep bed of granular material, resulting in a clean product stream (the filtrate). Media filters are typically capable of removal efficiencies in the order of 95% of particles 2 pm or larger and 98% of particles 5 pm or larger.

As with most deoiling equipment, the hydrocarbon removal efficiency of the filter will be a function of the hydrocarbon droplet size in the feed. However for most applications media filters can produce a water effluent with a hydrocarbon content of less than 10 mg/l dispersed hydrocarbons, often achieving less than 5 mg/l.
It is important to note that media beds do not operate by surface filtration. Surface filtration is the separation mechanism where the particles or droplets to be filtered from the water removed become wedged in the spaces between the grains of media. Surface filtration in a deep bed filter is undesirable as it will quickly result in blockage of the top layer of the bed and the capacity of the subsequent layers of the media bed will not be effectively utilised. The pore openings between the granular media grains are relatively large compared to the suspended particles, allowing the particles to pass into the bed of the filter. Inside the bed the suspended particles become trapped by first intercepting, then attaching to the media. Thus the suspended particles and droplets in the feed stream are removed within the body of the media bed, not on the surface.

8.14.1.2. Sand filters
The simplest form of media filter is the sand filter. The disadvantage of a sand filter is that when the filter is cleaned by backflushing, the sand particles will tend to segregate with the smallest sand particles concentrated in the uppermost layers, Whilst this segregation is ideal for a filter in which the water flows upwards, in the majority of media filters the water flow is downwards. With down flow operation this surface layer of fine sand will block more rapidly than larger sand particles, reducing the length of the filtration cycle. This segregation of the sand particles during the backwash operation is partly alleviated through the use of multimedia filters.

8.14.1.3. Multimedia filters

A typical multimedia sand filter design is illustrated in Figure 8.14.1.
Vent
U

Oily water feed

Feed distributer

Anthracite media layer Garnet media layer Clean water outlet Filtrate collection

Figure 8.14.1 Multimedia down flow sand filter

SIPM Drorlrnji Moiirrrtl. EP 93-1315, Rev I 1. NIIV 1993. Frlr iirririe = 814DEEP DOC

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8.14 Dispersed hydrocarbons - Deep bed media filtration
In a multimedia filter, two or more media with a different grain size and density are used with the denser particles having the smaller grain size. During backwashing, the two media will segregate with the larger sized, less dense media forming a layer above the dense, small sized media. Within each media layer there will still be size segregation, however the overall performance of the filter will be improved. The larger particles on the surface of the filter will minimise blockage of the surface layers, allowing more of the bed depth to be utilised for filtration. 8.14.1.4. Nut shell media filters (Hydromation and Wemco Silver Band) An alternative filter media is crushed nut shells, such as the Hydromation filter (walnut shells) or the Wemco Silver Band filter (walnut/pecan shells). This media is preferentially wetted by the water phase which makes the media easier to clean during the backwash cycle and improves the long term performance of the filters when used for the filtration of hydrocarbons. Because of their potentially superior performance in deoiling waste water, the Hydromation and Wemco Silver Band filters are recommended over conventional media filters for the removal of dispersed hydrocarbons from water. These filters are discussed in more detail in section 8.14.7. 8.14.1.5. Oleophilic filters Another alternative filter media are oleophilic materials as used in the InPlant or Serep filters. The filter media (produced by Serep, France) takes the form of small ceramic chips which have had an oleophilic agent grafted on their surface, allowing the filter media to be preferentially wetted by hydrocarbons. It would be expected that such a media would tend to capture hydrocarbons more efficiently and have a higher hydrocarbon carrying capacity than other media. The filter is claimed to be able to achieve 15 mgll in the effluent with a feed of 500 mg/l hydrocarbons and 50 mg/l solids. An InPlant trial filter was tested in Oman with encouraging results. InPlant have since been taken over by North American Technology. However, the long term performance of the filter media is not known, especially the possible effect of treatment chemicals on the media (e.9. deoilers, corrosion inhibitor) and the ability of the media to resist fouling by hydrocarbons over long periods of operation. 8.14.1.6. Cleaning of media filters Over the length of the filtration cycle, the media bed of the filter will become progressively blocked by accumulated solids and hydrocarbons. Eventually the media bed will require cleaning, either when the flow rate through the filter falls to an unacceptable level, when the pressure drop across the filter becomes excessive or when the quality of the filtrate deteriorates. Cleaning of media filters is generally conducted by taking the filter off-line and fluidising the media bed with a back flow of clean water, allowing the accumulated hydrocarbons and particles to be washed away. The cleaning of the media is enhanced by collisions between the fluidised media and is often assisted by sparging air or gas into the filter to scour the media. Hot water backflushing and/or surfactant chemicals may be used to assist the removal of hydrocarbons from the media. Normally clean, filtered water is used for backwashing and provision may have to be made to store a suitable quantity of backwash water. Alternatively clean water may be taken from the discharge of another on-line fitter, however this will require the filter package to effectively have two spare filters, one being cleaned and one providing water for backflushing. The crushed nut shell media filters do not require clean water for backwashing and their special cleaning arrangements are discussed in more detail in section 8.14.7.

8.14.2.

Performance variables

8.14.2.1. Hydrocarbon droplet size and solid particle size
In general terms, the larger the size of a hydrocarbon droplet or solid particle, the greater the probability that it will be removed by a deep bed media filter. This is illustrated in Figure 8.14.2 where it can be seen that the separation efficiency rises with particle size. Media filters are typically capable of removal of 95% of particles 2 pm or larger and 98% of particles 5 pm or larger.

Puae 8-14-2

SIPM Deoilinji Mwirurl, EP 93.1315. Rev 1.1, Nuv 1993. File ntrrne = X14DEEP.DOC

8.I4 Dispersed hydrocarbons - Deep bed media filtration

0

5

10

15

20

Particle size (pm) Figure 8.14.2 Typical separation performance of a multimedia filter

However, the performance of a filter must be considered in relation to both particle removal efficiency and overall filtration efficiency. Particle removal efficiency is a measure of how efficiently a filter removes a particle or droplet, regardless of the throughput through the filter. Filtration efficiency takes the flow rate through the filter into consideration. For example, large solid particles or droplets entering a media filter will be quickly removed in the uppermost layer of the media bed, leading to surface filtration. The surface layer will be very efficient at removing incoming particles, hence will have a high particle removal efficiency. However, the actual flow rate through the surface layer will be restricted, resulting in a low overall filtration efficiency. This behaviour is illustrated in Figure 8.14.3. It can be seen that above a certain ratio of particle diameter to media diameter, surface filtration effects will dominate and although the particle or droplet removal efficiency will continue to rise, the overall filtration efficiency will fall.

5

0

Thus, for a given media grain size, there will be an optimum feed particle or droplet size that will be efficiently filtered without inducing surface filtration. As an indication, for a media Particle diameter I Filter grain diameter bed of spherical particles, the largest particle H75026127P Figure 8.14.3 that can pass into the bed has a diameter of Particle removal efficiency and about one seventh (117) of the diameter of the filtration efficiency vrs ratio of feed media particles. Thus the feed to a filter particle or droplet size to filter media size consisting of 0.5 mm sand particles should not contain particles or droplets larger than 70 microns. In general it is recommended that particles or droplets larger than 100 pm are not allowed to enter the filter. This particle size corresponds to the size of solid particle or oil droplet that is readily removed by relatively simple upstream equipment such as a plate pack interceptor.

8.14.2.2. Flow rate
A filter should not be operated above its recommended maximum flow rate. Operating a filter at capacities above the design flow rate will raise the velocity though the open pores in the media bed. This will tend to detach the particles and hydrocarbons captured in the media bed and carry them through the bed into the filtrate, resulting in a deterioration of the filtrate quality and a shortening of the length of the filtration cycle.

8.14.2.3. Length of filtration cycle
The length of the filtration cycle for a filter is determined by either an unacceptable rise in differential pressure across the filter as the media bed becomes blocked or through excessive levels of contamination in the filtrate. For the filtration of solids, the rise in the pressure differential across the filter is likely to be limiting, while for the filtration of dispersed hydrocarbons the quality of the filtrate is likely to
SIPM Dmilrnl: Moriuol. EP 93-1315, Rev 1.1. Ntrv 199.7. File mime = XIlDEEPDOC

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8.14 Dispersed hydrocarbons - Deep bed media filtration
be limiting. It should be noted that when differential pressure is the limiting factor, the length of the filtration cycle will decrease dramatically with increasing flow rate as the increasing flow rate has a double impact. Firstly, forcing a higher flow rate through the filter will itself result in a higher pressure drop. Secondly, the higher flow rate will mean that the rate of solids entering the filter will be higher, blocking the filter more rapidly. Thus a doubling of the flux rate through the filter can lead to a four fold reduction in the length of the filtration cycle for a differential pressure limited filter.

8.14.2.4. Inlet hydrocarbon and solids concentration
Media filters are not tolerant of high concentrations of hydrocarbons or solids in the feed. High concentrations of hydrocarbons in the feed will tend to coalesce into larger droplets, increasing the probability that the hydrocarbons will be trapped in the surface layers of the bed, rapidly blocking the filter. The acceptable inlet hydrocarbon content is a compromise between the length of the filtration cycle and the nature of the hydrocarbon. Multimedia filters are claimed to be suitable for feed hydrocarbon concentrations in the order of 100 mg/l, however it is recommended that the inlet hydrocarbon content is normally limited to the order of 30-50 mg/l. Crushed nut shell media filters are suitable for hydrocarbon concentrations in the order of 100-150 mgA as they are more easily cleaned. High solids concentrations have a similar surface filtration effect due to bridging. A number of solid particles can wedge together, effectively bridging over and blocking the pores in the media bed. The solids concentration in the feed should typically be less than 50 mg/l.

8.14.2.5. Hydrocarbon characteristics
The physical characteristics of the hydrocarbon will have a significant effect on the length of the filtration cycle. Heavy oils are more likely to block the surface layers of the filter, shortening the filtration cycle. Similarly, waxy or fouling hydrocarbons will reduce the length of the filtration cycle and will shorten the expected useful life of the filter media. In some cases, filters can become clogged by oil accumulation and cannot be cleaned by backwashing. In other cases the filter media can be bound together by the fouling, collecting the media into “mudballs”.

8.14.2.6. Vent stream
Depending on the filter configuration, larger hydrocarbon droplets or gas bubbles will tend to rise and collect in the top of the filter vessel, This accumulation is removed by maintaining a small flow from a vent at the top of the filter vessel. The flow rate of this vent stream is usually manually adjusted on the basis of operational experience. A suitable flow path must be identified for the recycling of any vent stream back to the process.

8.14.2.7. Treatment of backwash water
During backwashing a relatively large reject stream is generated containing the filtered hydrocarbons and solids. The backwash stream cannot be recycled directly to the process as the solids would tend to accumulate in the process system. Instead the backwash stream is generally directed to a clarification vessel which allows the solids to settle and the hydrocarbons to rise. Separated hydrocarbons and accumulated solids/sludge are periodically removed from the clarification vessel. The clarified water can be recycled to the process. The volume required in the clarification tank may be a undesirable weight penalty in an offshore installation. The volume of backwash water requiring clarification could potentially be reduced by passing the backwash stream though a solid/liquid hydrocyclone to remove the solids. The solids/water stream from the cyclone underflow could be directed to a smaller clarifier while the hydrocarbon/water overflow stream could be recycled to the process. Alternatively, consideration should be given to the crushed nut media filters which have significantly lower backwashing requirements.

8.14.2.8. Chemical filtration aids
Coagulants and flocculants are often used upstream of filtration packages to improve the filtration performance. Section 8.4 discuses coagulation and flocculation in more detail. When using chemicals, care must be taken to screen for adverse interactions between the injected chemicals and the filter media or other chemicals in the water stream. Examples of detrimental
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SIPM Droilinh. Mtri~rtcrl. EP 93-1315, Rev 1.1, Nvv 1993. Filr nomr = Xf4DEEP.DOC

8.14 Dispersed hydrocarbons - Deep bed media filtration
interactions that have occurred in practice include; Formation of gel like polymers due to interaction between the injected polyelectrolyte and residual polymers in the production water (from an enhanced recovery scheme). Precipitation of ferric salts has been found to be detrimental to the performance of the crushed nut filter media.

8.14.3.

InstallatiotVConfiguration

8.14.3.1. Process location

As media filters are not tolerant of high hydrocarbon or suspended solid concentrations in the feed stream they are generally used as the second or third stage of water treatment. As previously discussed, it is recommended that upstream equipment should be designed to remove hydrocarbon droplets and solid particles larger than 100 pm. Course strainers (100 pm) should also be installed on the backwash system to prevent blockage of the filter distribution and collection systems.
8.14.3.2. Pressure drop The pressure drop across a clean media filter is typically in the order of 0.4 bar. When used for filtering solid particles the pressure increase over the filtration cycle is normally in the order of 0.3 to 1.4 bar. When the filtration cycle is dominated by hydrocarbon removal, the pressure increase is generally at the low end of this range when hydrocarbon breakthrough into the filtrate occurs. 8.1 4.3.3. Packaging Media filters are typically packaged into vertical pressure vessels. Suitable distribution and collection internals are required to ensure an even distribution of the water flow though the media bed. One standby filter should be provided to be brought on-line when other filters are backwashed or shutdown for maintenance. When specifying a filtration system, it should be remembered that in addition to the filter vessels themselves, provision may be required for a clarification tank for the backwash water and a storage tank to store clean filtered water to perform the backwash.

8.14.3.4. Size, Weight and Capacity
Figure 8.14.4 gives the typical operating weight for a skid mounted packaged deep bed filtration system for the treatment of oily water. The figure may be used for both dual media filter systems and crushed nut shell filter designs. However, additional weight allowance should be added as required for auxiliary systems such as chemical injection facilities, backwash water storage and clarification tanks.
350
300

0) .-

- 200 g
(u

3 250
C

p .E

-

t

150

0" 100
50

0
0
100 200

300

400

500

600

700

800

900

1000

1100

1200

1300

1400

Capacity (mYh)

Figure 8.14.4 Operating weight of dual media or crushed nut deep bed filtration systems

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8.14 Dispersed hydrocarbons - Deep bed media filtration
8.14.4.

Design guidelines
The following guidelines can be used for indicative sizing of downflow multimedia filters for the filtration of oily water. Higher flux rates are possible for sea water filtration duties (see SlPM Water Injection Manual, Report EP-63600). Guidelines for crushed shell filter media designs are given in section 8.14.7.
0

Flux rate through filter: 20 40 (m3/h)/m2 Accumulated hydrocarbon capacity of filter bed before cleaning: 40 kg/m2 Accumulated solids capacity of filter bed before cleaning: 20 kg/m2 Maximum recommended continuous hydrocarbon feed concentration: 30 - 50 mg/l Multimedia backwashing water flow: 40 (m3/h)/m2 for 10 to 30 minutes

-

When filtering oily water, the dirty backwash water is generally recycled to the process after the hydrocarbons and solids are removed. The capacity of the filtration package has to be sufficient to accommodate this recycling flow. The frequency of backwashing should be such that there is sufficient time in the clarification tank to allow solids and hydrocarbons to settle from the backwash water and for clarified water to be pumped away before the next filter backwash.

Figure 8.14.5 illustrates a typical control scheme for a deep bed filter system. Each filter is flow controlled by a flow meter and control valve on the outlet of the filter. This control system should ensure that all filters are operating with the same load. This is particularly important when a clean filter is brought on line, otherwise the clean filter will tend to rob the flow and over-flux, shortening the subsequent filter cycle.

b
n76mmw

8.14.6.1. Backwashing control During the backwash cycle the media bed is fluidised. The degree of fluidisation is a function of the density and the viscosity of the backwash fluid, both of these variables being functions of the backflush fluid temperature. The optimum backwash flow rate to give sufficient fluidisation without excessive media loss should be determined for the range of backwash fluid conditions, The backwash fluid flow rate should be measured and controlled at the appropriate rate. If backwash fluid conditions are likely to change significantly (e.g. wide temperature variations) then automatic adjustment of the backwash flow rate setpoint may be warranted. 8.1 4.6.2. Media loss The rate of media loss from the filter is a function of the frequency of backwashing and proper control of the backwash cycle. Media is also lost by attrition of the media particles. Typical media loss is in the order of 10% per year. 8.14.6.3. Operating experience A large number of deep bed media filters are commonly used throughout the petroleum industry for the filtration of sea water for water injection. However installations for the filtration of oily water are not as common. Table 8.14.1 summarises the operating experience with deep bed media filters for the treatment of oily water for a range of Shell installations and trials.

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8.I4 Dispersed hydrocarbons - Deep bed media filtration
8.14.7.
Crushed nut shell deep bed media filters

8.14.7.1. General
Crushed nut shell filters are a form of deep bed media filter, utilising crushed walnut or pecan nut shells as the filter media. They are of particular interest to the filtration of oily water due to the hydrophilic nature of the filter media which ensures the filter media is preferentially water wetted. This allows the hydrocarbons that are filtered from the feed stream to be relatively easily removed during backwashing. Backwashing is performed using the unfiltered feed stream as the fluidising medium, eliminating the requirement for a storage tank to store filtered water for backwashing. The flow rate of backwash water is significantly lower than for conventional deep bed filter designs, minimising the size of additional facilities required to deal with the dirty backwash water.

No additional media cleaning facilities such as gas scouring or chemical addition are required. As the media is efficiently cleaned there should be no requirement for media replacement except to cover a 1015% annual media loss due to attrition.
At the time of writing there are no crushed nut media filters being used for the filtration of sea water. SIPM are planning to evaluate this aspect in 1994 to determine whether a crushed nut shell filter could be used for sea water filtration in the early years of a field development, then be switched to produced water service as the field matures.

8.14.7.2. Hydromation
The Hydromation filter is illustrated in Figure 8.14.6. During the filtration cycle the filter acts as a normal deep bed filter, using crushed walnut shells as the filter media. During the backwash cycle the filter is shut in and the media scrubber pump used to fluidise, then circulate the filter media downwards through the external media scrubber. The media scrubber contains a wedge-wire strainer that allows small particles and hydrocarbons to pass to the backwash discharge, while the filter media is returned to the filter vessel. The turbulence and collisions generated during the backwash recirculation cleans the filter media.

t
1

I

1P
I

Air/gas vent
Access hatch

vation ports

Figure 8.14.6 Hydromation crushed shell deep bed media filter

After the backwash the flow through the filter is reversed and the filter bed reforms. The filter is then operated for a short period on recycle to wash the contaminated backwash water out of the filter bed. The filter is then clean and ready to be brought back on line.

8.I4 Dispersed hydrocarbons - Deep bed media filtration
The Hydromation filter is available in two configurations. The down flow configuration illustrated in Figure 8.14.6 for capacities up to 350 m3/h and a radial flow configuration for capacities up to 1025 mVh. The radial flow configuration is more space and weight efficient, but is only suitable for relatively high flow rates.

8.14.7.3. Wemco Silver Band
The Wemco Silver Band filter is illustrated in Figure 8.14.7. During the filtration cycle the filter acts as a normal deep bed filter, using a mixture of crushed walnut and pecan nut shells as the filter media.

t

Media support screen

-rC Dirtywater

inlet

Contaminant discharge
IC-

Drain

-.+.
Figure 8.14.7 Wemco Silver Band crushed shell deep bed media filter

n water IC outlet

The backwashing and media cleaning system is similar to the Hydromation filter with the clean water outlet valve shut and the filter media recirculated by a pump past a separator screen. The screen allows the solids and hydrocarbons to exit the filter but retains the filter media inside the vessel. The Silver Band filter has the separator screen built inside the filter vessel itself. After the backwash the recirculation is stopped and the filter bed reformed. The filter is then clean and ready to be brought back on line. The Wemco Silver Band filter has been tested at the OWTC. The full test report (EP 91-2152) can be obtained from SIPM on request. The filter was found to consistently achieve in the order of 10 mg/l hydrocarbon in the effluent from a 200 mg/l feed stream.

8.14.7.4. Performance characteristics
The performance characteristics for either of the crushed shell filters is generally similar to the other deep bed filters discussed. The major exception is the performance of the filter in response to hydrocarbon feed concentration and hydrocarbon characteristics. During the actual filtration cycle, the response of a crushed shell filter is not likely to be different to other media filters. High hydrocarbon concentrations are likely to result in surface filtration and a shortening of the filtration cycle, especially with heavy crude oils. However, due to the hydrophilic nature of the filter media, the crushed shell filters are more likely to be efficiently cleaned and to return to good performance after the regeneration cycle. This ability to deal effectively with hydrocarbons in the feed makes the crushed shell filters more suitable to deoiling duties than other deep bed media filters. Problems have been experienced when ferric sulphide salts have precipitated in the filter due to the mixing of different water sources. The precipitate attaches to the filter media and reduces the ability of

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8.14 Disoersed hvdrocarbons - DeeD bed media filtration
the filter media to regenerate. If the media is contaminated in this manner an acid wash can be used to remove the precipitate. Further precipitation can be prevented by small quantities of acid injection.

8.14.7.5. Design guidelines
The following guidelines can be used for indicative sizing of crushed shell media filters for filtering oily water. Flux rate through filter: 25 30 (mVh)/m* Maximum recommended continuous hydrocarbon feed concentration: 150 mgh Backwashing Total backwash cycle time Backwash water volume 8.14.7.6. Size and weight comparison The size and weight of a crushed shell filter system is approximately the same as an equivalent dual media filtration system. Thus Figure 8.14.4 may also be used to estimate the operating weight of a crushed shell filtration system for the treatment of oily water. The crushed nut shell filters do offer some external weight savings in that a clean backwash water storage tank is not required and that due to the smaller quantity of backwash water generated, the backwash water clarification tank does not need to be as large as required for an equivalent dual media system.

-

- 22 minutes (Hydromation) - 14 minutes (Silver Band)

- Typically 1 .O to 1.5 % of throughput

SlPM Deoiling Mrtnuctl. EP 93-1315, Rrv 1.1. Nov 1993, File nonrr = XI4DEEP.DOC

Puae 8-14-9

Location

Equipment

Oman. Mina al Fahal Hydromation oil terminal and Marmul, Suwaihat and Qarn Alam onshore production stations Oman, Mina al Fahal oil terminal and Manu1 onshore production station The Netherlands. Schoonebeck Spain, Shell Espana San Carlos de la

Inlet Outlet Hydrocarbon Date Field trial or Installed equipment hydrocarbon concentration removal (date of equipment Installation concentration (rngl) efficiency in brackets) (mgl) (MaF) 76 to 95% Equipment field trials, results 1992 (MaF) 32 to 154 (MaF) 5 to 17 (M) 157 (M) 24 (M) 85% given lor Mina a 1 Fahal (MaF), m 6 . 9 w Lsm!.YQ Marmul(M), Suwaihal & and (a) 3 to i o (a) 85 to 95% Qarn Alam (Q). Note that all (Q) 54 to 62 results are given in ppmv 1992 (MaF) 38 m g l
(M) 4 14 mg7

Solids handling

Use of chemicals

Comments

Reference

InPlant lilter Equipmentfield trials, results using given lor Mina a 1 Fahal (MaF) oleophilic filter and Marmul (M media Hydromation Field tnals with Hydromation filter. Field trial on tanker vessel 'Delta', Castellon field

(MaF) 4 mgl
(M) 55 m y l

(MaF) 89%
(M) 85%

lot used Typical for all fields Inlet 9 lo 69 m d Outlet 7 to 30 mgfl 11 to 71% 01 solids removed (MaF) 34 rngl lo lot used 16mgnie 53% reduction

4 pm range and 95% of particles greater than 4 pm. It is suspected that lor one location corrosion

Filter will normally remove 85% 01 particles in 2 lo 2.7.2.a

inhibitor reduced the performance of the filter, through not in other locations. In this one case the media had lo be replaced. During the MaF trials. best results were obtained 2.7.2.k when lresh water was used lor backwashing. Unit suffered from mechanical problems. Mechanical problemsconsidered reason lor high Marmul oullel concentrations, lor some periods outlet oil concentrationsless than I O mg!l were obtained. 2.7.2.h Excellent performance lrom trial unit, oil concentrations reduced from 100 or 200 ppm lo lower than 1 ppm. Performance01 the Mer was found to improve with 2.7.2.1 the addition 01 5 lo 10 ppm 01 Willloc polymer. Filter design allows for the continuous draw on and 2.7.2.b cleaning 01 the filter media. However it was tound that the oil concentration in the outlet water was loo variable. 1993deoiling Performance of sand filter deteriorated over a period 01 2 years. Improved abet chemical cleaning questionnaire 01 filler media 1993 deoiling Water disposed of in disposal wells. Initial target was less than 3 m g l oil. Disposal lormation found questionnaire to be tolerant thus performanceof lilter has not been optimised. This reduces use of chemicals.

1984 20 lo 500 rngl

0 to 4 mgA

Average 01 95% I O to 74 ppm solids. reduced to 0 4 to 6 ppm Average 01 79% Not known

lot used

Hydromation

1985 33 mgl 1984 120103M)ma/l
I

Denmark, Fredericia Dynasand relinery continuous /filter onshore oil field heavy oil field

I

Field trial with various mixed refinery waste waters.

7 mgl 5 ma4 with use 101 chemicals 1310165ma4
I

I

kA%
Not relevant
80%

I

'es, see ornments

IAveraoe removal 00 ppm poly!lectrolyte of TSS - 67% Not known Typically 65 mg/ in feed
401 used

1993 1 to l 5 m g l Typically 5 mgl I993 15to225mgl Typically 75

1 rngl

mdl

Typically 15 rngl

tOlo170mgl

Jot used

SIPM Droiling Monuul, € P 9.1-11115. Rev I .I. N w 1993, File nome = TABX-I4

,oc

Table 8.14.1 Page 1 of 2 Deoiling equipment summary table Deep Bed Media Filtration

-

-

Location

Columbia. Dina onshore oil field The Netherlands, NAM. East NetherlandsGas Fields, Drente, Twente Brunei, Seria oil terminal OWTC

Field trial or installed Date Inlet Outlet Hydrocarbon Solids handling Use of equipment hydrocarbon concentration removal chemicals efficiency (date of equipment installation concentration (mgn) in brackets) (in@) L'eau Claire Installed equipment, (1985 and 1993 10 to 100 mgl 1 to 8 mgl 94% Typically 20 mgl 1 ppm 01 polyin feed electroiyle added and 1991respectively) Typically 50 mgl Typically 3 mgl to filter feed Depremont 7 to 40 mg/l Not relevant Normally20 to No chemicals Wemco Silver Installed equipment (1992) 1993 10 to 250 mgl Band Typically 25 mgl Typically 16 m@l 25 mgl in leed. used may of 50 mgA Equipment

Comments

Reference

1993 deoiling river. Filters perform well given that upstream questionnaire facilities are undersized. Thought that filter requires higher feed pressure to 1993deoiling ensure bed compaction and better performance. questionnaire

Must achieve less than 5 ppm for discharge into

I

Serck Baker

1Wemco Silver IEauiDmenttest centre

I

InstalledeauiDment (1985) . . . ,

1993 10 to 20 moll Typically 1 ;

I

I

Tvoicallv 5 mail
I. I

-

Not relevant
I.

Not known

See comments

Coaaulationand flocculation chemicals used in ]upstream flocculatiodflotation unit. Filter optimisedat 200 mg/l in feed, consistently gave below 15 mgl in product. Performance generally good. Presence of demulsifier caused very poor performance(D 100 mgll in product) but concentrationof demulsifier was far higher than the residual levels of demulsifier that would IvDcally .. . be lpresent in the feed.

1993 deoiling lguestionnaire

,

causedvery poor increased wiih solids, however perlormance. See comments not fully investigated

I

I

I

Table 8.14.1 Page 2 of 2 Deoiling equipment summary table Deep Bed Media Filtration

-

-

8.14 Dispersed hydrocarbons - Deep bed media filtration

INTENTIONALLY LEFT BLANK

PURC8-14-12

SIPM Deoilitig Motiud. EP 93-1315. Rev 1.1. NIJV199.9, File tiotne = XI4DEEP.DOC

8.15 Dispersed hydrocarbons - Cartridge filters
8.15. 8.15.1. CARTRIDGE FILTERS Introduction
Cartridge filters consist of hollow cylindrical filter elements. The waste water normally passes from the outside of the cartridge through the filter medium and the clean filtrate leaves from the centre of the cartridge. Many materials are available to form the filter medium including glass fibre, pleated paper, polypropylene, woven metal mesh, woven wool or cellulose fibres, sintered metals and moulded fibres. The filter medium can be designed to provide surface filtration only or the structure may be arranged to give a depth filtration effect. The primary advantage of cartridge filters is their ability to provide a large filtration surface area in a relatively small package. While cartridge filters are used extensively for the filtration of solids from liquids and gases, they are not commonly used for the removal of dispersed hydrocarbons. Hydrocarbons cannot be effectively removed from the filter media by simple backwashing and the cost of regular cartridge replacement can be excessive. As such, cartridge filters are more commonly used as guard or polishing filters, designed to remove the small quantities of hydrocarbons and solids that may pass through upstream deoiling equipment. For more detailed information on cartridge filtration systems as used for sea water filtration the user is referred to the Water Injection Manual EP-63600 (Update expected by mid 1994).

8.15.2.

Performance variables

8.15.2.1. Hydrocarbon droplet and solid particle size Cartridge filters are capable of removing hydrocarbon droplets and solid particles down to very small sizes. A common performance specification is 98% removal of particles down to 2 pm. Users should be aware of the difference between absolute and nominal filter ratings. An absolute filter will ensure all particles larger than the absolute rating will be removed by the filter. A nominal rating indicates the median particle size removed, however a percentage of larger particles may still pass through the filter. Cartridges are available with absolute ratings down to 0.6 pm.

8.15.2.2. Inlet hydrocarbon and solids concentration
The replacement of disposable cartridge filters incurs a significant operating cost. Thus disposable cartridge filters cannot be used for high concentrations of either hydrocarbon or solids, where the life of the cartridge would be too short. The appropriate dispersed hydrocarbon or solids content in the feed to a cartridge filter would typically be 5 mg/l or lower. 8.1 5.2.3. Pressure drop The typical pressure drop across clean cartridge filters is in the order of 0.3 bar. This increases to the order of 1.4 bar when the filter is dirty and at this point the cartridge must be cleaned or replaced. If the pressure drop across the filter becomes too high the filter element may collapse.

8.1 5.3.

Insta I lat io n/Conf igurat ion

8.15.3.1. Process location As previously discussed, due to the cost of replacing cartridges, cartridge type filters are normally used at the end of the water treatment process where the hydrocarbon and solids loading is very low. In many cases, they are used as guard filters to provide a last line of defence in case of failure of upstream deoiling equipment. 8.1 5.3.2. Packaging To provide the required filtration area, a number of cartridges are packaged together on a tubesheet and placed in a vertical pressure vessel. The system should be designed for simple and quick replacement of

8.15 Dispersed hydrocarbons - Cartridge filters
the filter elements.

8.15.4.

Design guidelines
The sizing of a cartridge filtration system will vary significantly with the filtration rating of the filter elements. Relatively coarse filter elements will have a much higher flux rate than finer filter elements. Vendors should be contacted to determine the characteristics of suitable cartridges.

8.I6 Dispersed hydrocarbons - Pre-coat,filtration
8.16. 8.16.1. PRE-COAT FILTRATION Introduction
Pre-coat filters offer the possibility of producing water of a very low residual suspended solids content with equipment operating at a high throughput for its size and weight relative to media filters. Pre-coat filters are normally only economically viable for treating water which contains relatively low levels of dispersed oil and solids, or where stringent water quality specifications have to be met. They have found application for the removal of the final traces of solids and hydrocarbons from production water, prior to water softening and conversion to steam for enhanced recovery applications.
A typical pre-coat filter consists of a pressure vessel housing leaves or “candles” fabricated from a coarse metal mesh. The leaves or candles support a finer 20-100 pn mesh fabricated from woven fabric or stainless steel. A slurry of filter aid, normally diatomaceous earth or Perlite, is circulated through the filter to build up a layer of pre-coat.

Once the pre-coat layer is established the oily feed stream can be introduced to the filter. A slurry of filter aid (known as “body feed”) is continually added to the feed to ensure that the filter surface is continuously renewed and remains permeable. The function of the filter aid is to provide a permeable surface structure to allow the continuous accumulation of solids and hydrocarbons. Without filter aid the filter would be quickly blinded by the accumulating solids and hydrocarbons in the filter cake. The end of the filtration cycle is reached when the differential pressure across the filter reaches a predetermined maximum or when there is no more physical space inside the filter to deposit the filter cake of solids, hydrocarbons and filter aid. The filter is taken off line and the accumulated filter cake removed from the filter. The filter cake can be removed from the supporting mesh by a variety of methods such as water sprays, backwashing, pneumatic pulses etc. Once the filter cake is removed and the filter is clean the filtration cycle can be restarted. Normally, dispersed hydrocarbons are difficult to filter as the hydrocarbon droplets will deform under pressure and blind the filter. The advantage of the pre-coat filter is that the body feed helps maintain the permeability of the filter cake under these conditions. The main disadvantages of the pre-coat filters is the inconvenience of handling the dry and slurried filter aid, the operating cost of purchasing the filter aid and the potential disposal problem of the oily filter cake.

8.16.2.

Performance variables

8.16.2.1. Inlet hydrocarbon and solids concentration
Pre-coat filters are generally only used for polishing duties. The concentration of solids in the feed stream should be less than 5 mg/l while the concentration of hydrocarbons should be less than 15 mg/l, preferably less than 10 mg/l. 8.16.2.2. Rate of body feed the rate of body feed addition, as illustrated in Figure 8.16.1. At low levels of body feed there will not be sufficient filter aid to provide a permeable filter cake. The throughput may actually decrease as the small amount of body feed only increases cake thickness without improving permeability. As more body feed is added the throughput of the filter will start to rise. Eventually the throughput will reach a maximum where the addition of

p y
c

5 L
(u

2

i i
c

-

c

8.16 Dispersed hydrocarbons - Pre-coat filtration
optimum rate of body feed should be determined from field trials. 8.1 6.2.3. Effectiveness of pre-coating The pre-coating of the filter serves several purposes. As well as ensuring a clean filtrate, the pre-coat protects the underlining filter screen from fouling and ensures a more effective backwash at the end of the filtration cycle. Trials have indicated that satisfactory pre-coating can be quite difficult to achieve. Variables that will affect pre-coating include the flow rate used during the pre-coating procedure, the concentration of filter aid in the pre-coating slurry and the flow patterns inside the filter vessel during the pre-coating. Baffles can sometimes be used to alter the flow characteristics inside the filter to give a more satisfactory precoat. 8.16.2.4. Filter aid The most common filter aids used are diatomaceous earth (e.g. Celite) or Perlite. Diatomaceous earth gives longer filtration cycles than Perlite, but is more expensive (although less is needed). Perlite has a lower bulk density which increases the storage space required for the dry filter aid.

8.16.3.

Installation/Configuration

8.16.3.1. Process location As pre-coat filters are not tolerant of high hydrocarbon or suspended solid concentrations in the feed stream they are generally used as a final stage of water treatment. 8.16.3.2. Guard filters When using pre-coat filters there is always a possibility of some of the pre-coat material passing through the filter. It is recommended that guard filters (typically cartridge type) are installed to protect the downstream environment from poor pre-coat filter performance or any accidental breakthrough of filter aid. The guard filters will also give an immediate indication of problems with the pre-coat filters by a rapid rise in differential pressure.

8.16.4.

Design guidelines
The following guidelines can be used as initial design parameters for a pre-coat filtration system. Flux rate through filter for produced water: Diatomaceous earth bulk density: Perlite bulk density: Typical diatomaceous earth pre-coat: 1.2 - 2.5 (m3/h)/m2 Dry powder, 110 - 240 kg/m3 Wet filter cake, 240 - 320 kg/m3 Dry powder, 60 - 90 kg/m3 Wet filter cake, 110 - 130 kg/m3 2 of filter area 100 - 150 kg / 100 m

8.16.5.

Operational considerations

8.16.5.1. Disposal of filter cake
A suitable method to dispose of the filter aid must be included in the design. The filter cake from the filters will be contaminated with solids and hydrocarbons and cannot be simply discharged or recycled.

8.16.5.2. Maintenance of flow The pre-coat and filter cake must be held on the mesh supports at all times by maintaining a positive flow through the filter, particularly when switching from the pre-coat cycle to the filtration/body feed cycle. In the event of loss of positive pressure on the filter cake (e.g. power failure) the filter contents will have to be dumped and the filters re-coated before resuming filtration.

PURC

8-16-2

SIPM D a d i n ( : Moiiiiiil, EP 93-1315, Hrv 1 . 1 . Nov 1993. File mime = 816DIAT.DOC

8.I6 Dispersed hydrocarbons - Pre-coat.filtration
8.16.5.3. Exposure to filter aid, fire, handling, dust
Storage and handling facilities for filter aids must consider the special requirements for storing dry powders, such as the storage volume requirements (filter aids have a low bulk density) and suitable systems and procedures to minimise dust exposure (health and explosion risks). Diatomaceous earth is considered hazardous as it can give rise to fibrosis from long term exposure due to its cristobalite content. Skin and eye irritation are also possible due to its high pH (8-1O).The American Industrial Hygiene Association threshold limits set maximum operational exposure levels to airborne diatomaceous earth to 0.05 - 0.28 mg/m3. The corresponding maximum operational exposure level for Perlite is 2 - 4 mg/m3.

SIPM Droilinp Monlrril. EP 93-13l5. Rev I I . Nov 1993. Filr

iifiiiw

= X16DIAT DOC

P U ~ 8-16-3 C

8.1 6 Dispersed hydrocarbons - Pre-coat filtration

THIS PAGE HAS BEEN INTENTIONALLY LEFT BLANK

P U ~ 8-16-4 C

SIPM Deiiiliiig Miiiircol, EP 93-1315, Rev 1.1. N ~ I 1993. V File nilme = X16DIAT.DOC

8.I ? Dispersed hydrocarbons - Membranes
8.17. 8.17.1.

MEMBRANES

Introduction
Membranes act fundamentally like filters. Membrane processes cover microfiltration, ultrafiltration and nanofiltration. Microfiltration and ultrafiltration use porous membranes and separate on the basis of size, with droplets or particles larger than the pore size not passing through the membrane. Nanofiltration uses non-porous membranes and separates on the basis of selective solution and diffusion of a species through the membrane Figure 8.17.1 illustrates the typical operating ranges of the various membrane filtration processes.

t

I

I

I

I

I

I

I

I

0.00001

0.0001

0.001

0.01

0.1

1

10

100

1000

10000

Particle size (vm)

Figure 8.17.1 Range of membrane filtration processes

To separate hydrocarbons from water, membranes are operated in a cross flow configuration with the oily water flowing across the membrane surface. The cross flow configuration helps minimise fouling by sweeping hydrocarbons and solids along the membrane surface. The water at the membrane surface will preferentially pass through the membrane, producing a clean water permeate. The remaining concentrated hydrocarbon/water stream is known as the retentate or concentrate. As illustrated in Figure 8.17.2, membrane systems are normally operated with a recycle stream which can be up to 20 times the feed rate. This raises the hydrocarbon concentration of the stream feed across the membrane surface and reduces the flow rate of the reject stream that is withdrawn to remove the accumulating hydrocarbons. While membranes for oily water clean-up show considerable promise, the generally rapid decline in flux rates due to fouling and variable results in membrane cleaning have hampered their application..
H75117/11P

Treated water

I%ed

Recycle

- Reject stream
4

The results from the OWTC trials are summarised in Appendix L.

8.I7 Dispersed hydrocarbons - Membranes
8.17.2.
Performance variables

8.17.2.1. Hydrocarbon droplet size The pore sizes for microfiltration or ultrafiltration membranes is very small and will not allow hydrocarbon droplets to pass. However water (and dissolved hydrocarbons) will pass through the pores. As illustrated in Figure 8.17.1, very small hydrocarbon droplets can be separated from a water stream with a microfiltration or ultrafiltration membrane. Nanofiltration membranes are non porous and are thus completely independent of hydrocarbon droplet size. However, hydrocarbons can still potentially pass through the membrane by physically dissolving into the membrane and diffusing through. 8.1 7.2.2. Inlet and outlet hydrocarbon concentrations The tests at the OWTC indicated that the membranes were not particularly sensitive to inlet hydrocarbon concentration. Increasing the inlet hydrocarbon concentrations from 50 mg/l to 1000 mg/l resulted in rises in permeate concentration from the order of 5 mg/l up to a range of 10 to 15 mg/l. This performance indicating an ability to maintain a low outlet hydrocarbon concentration when faced with high inlet hydrocarbon concentrations is very encouraging. It should be noted that, as membrane systems typically utilise recycle streams, the concentration of hydrocarbons within the recycle loop will be already be significantly higher than the initial feed concentration. High levels of hydrocarbons in the feed may result in more rapid fouling, lowering the membrane flux rate and shortening the membrane life. To minimise the need to clean the membrane and to maximise the working life of the membrane, the concentration of hydrocarbons in the feed stream should generally be kept as low as possible. Membranes should be protected from slugs of pure hydrocarbon. When the reaction of the membranes to hydrocarbon slugs was tested at the OWTC, the membranes showed relatively small changes in the permeate hydrocarbon concentration, however, for several membranes the flux rates through the membranes dropped dramatically until the slug was cleared. 8.1 7.2.3. Dissolved hydrocarbons By definition, porous membranes should not have any effect on the levels of dissolved hydrocarbons in the permeate. In many cases, the dissolved hydrocarbon content in the permeate may be higher than the feed due to the recycle stream building up higher concentrations of dissolved hydrocarbons within the membrane unit. In some cases, porous membranes have achieved reductions in dissolved hydrocarbons. This effect may be related to the concentration of dispersed hydrocarbons remaining in the retentate altering the solubility of the hydrocarbons in the water phase. This effect may not be consistent enough for the reliable reduction of dissolved hydrocarbons. Non-porous membranes in which the water “dissolves” into the membrane may achieve some separation of dissolved hydrocarbons on the basis of different rates of diffusion through the membrane. However, to date, trials to specifically investigate the removal of dissolved hydrocarbons alone (as opposed to the numerous trials with dispersed hydrocarbons) do not appear to have been conducted. The SDI membrane design appears to have some potential for the separation of dissolved hydrocarbons and is being evaluated by Shell Expro. Membranes can potentially be used to assist the removal of dissolved hydrocarbons as part of the pervaporation process. This process is discussed in more detail in Chapter 9. 8.17.2.4. Membrane flux The flux across a membrane is a function of a number of variables, particularly pore size, water viscosity and pressure drop across the membrane. Fouling of the membrane will result in a gradual deterioration in the flux rate. At the current stage of development it is unlikely that vendors could provide a realistic flux rate given the operating conditions and allowing for fouling over the life of the membrane. The design of membrane systems must be based on a stable long term flux rate that can be expected from the membrane over a long period of operation. Current stable flux rates are too low to be economic when compared with other equipment. Flux rates of new, clean membranes or when tested with water
P U ~ 8C 17-2
SlPM Dcoiliiil: Miirircnl. EP 93-1315, Rev 1.1. Nov 1993, File nnrnr = X17MEMB.DOC

~

~~~~

8.I7 Dispersed hydrocarbons - Membranes

alone are misleading and cannot be used for design.

8.17.2.5. Temperature
In general, the flux rate through a membrane will improve significantly at higher temperatures. This variation in flux rate will have a significant impact on the required membrane area.

8.1 7.3.

Insta I lat ion/Conf igurat ion

8.17.3.1 Process location
The factors most likely to upset the performance of a membrane system are slugs of hydrocarbons and gradual fouling of the membranes from hydrocarbons and solids. Thus to obtain the best performance and life from membranes it is recommended that they be located as a final stage in a water treatment system for the removal of dispersed hydrocarbons. Upstream equipment should be designed to remove the majority of the hydrocarbons and solids and protect the membranes from slugs of hydrocarbons.

8.17.3.2. Pressure drop
Pressure drop requirements for membranes range from 1 to 5 bar. Excessive pressure drops should be avoided as they will tend to force impurities into the membrane, making cleaning more difficult.

8.17.3.3. Size, Weight and Capacity
As part of the Phase I and II OWTC membrane trials, membrane vendors were asked to provide information on the dimensions, weight, cost and utility requirements for membrane packages suitable for the treatment of 330mVh, 670mVh and 1330 m3/h of produced water (50,000 bwpd, 100,000 bwpd and 200,000 bwpd respectively). This information is included in the OWTC reports referenced in section 8.17.4. and may be obtained from SlPM on request. However, as the long term performance of these units has not been substantiated, these size and cost estimates cannot be supported.

8.17.4.

Membrane trials

8.17.4.1. Membrane trials at the OWTC
The following membrane trials have been conducted at the OWTC. Full reports are available from SlPM on request. Summaries of the performance of each of the membranes tested are given in Appendix L.
e

“Membrane filter trials with various oily waters at Orkney Water Test Centre Ltd”, Phase I, 15 April 1991, EP-no. 91-1017 The following four membranes were examined in the Phase I trials: Alcoa Petrolox, SDI, Stork-Wafilin and X-Flow. The report investigated the effect of the following variables on the performance of the membrane systems: Variation in oil type, concentration, droplet size and slugs of oil. Variation in water temperature and salinity. The effect of oil field chemicals, gas breakout, and scale forming compounds.

e

“Membrane filter trials with various oily waters at Orkney Water Test Centre Ltd”, Phase II, 20 September 1991, EP-no. 91-2152 The following three membranes were examined in the Phase I trials: WL Gore, Schelde Delta and SDI (modified since Phase I trials). The report investigated the effect of the following variables on the performance of the membrane systems: Variation in oil type, oil droplet size and slugs of oil. Variation in water temperature and salinity. The effect of oil field chemicals and scale forming compounds.

8.17.4.2. Membrane trials at the WTC
SlPM is currently sponsoring a membrane test program at the Wastewater Technology Centre in Canada. These trials are aimed at identifying fouling compounds, fouling mechanisms and membrane structures which resist fouling.

8.I7 Dispersed hydrocarbons - Membranes
Field trials may be arranged as part of a second phase of the project if promising membranes are identified.

9.I Dissolved hydrocarbons - Introduction

9.1.

INTRODUCTION
In many E & P operations, particularly offshore, both regulations governing hydrocarbon discharges and deoiling equipment design are based on the removal of only insoluble dispersed hydrocarbons from waste water. However, as illustrated in Chapter 2, waste water from hydrocarbon production facilities may contain significant quantities of dissolved hydrocarbons. In many land based installations, particularly in the refining and manufacturing industries, discharge regulations and environmental considerations frequently require the removal of both dispersed and dissolved hydrocarbons from effluent waters. There is speculation that similar standards may be applied to the discharge waters from E & P operations, including offshore installations. The following sections introduce and discuss the range of equipment available for the removal of dissolved hydrocarbons. Unlike the removal of dispersed hydrocarbons where the hydrocarbon and water phases are physically separated, the majority of the techniques used for the removal of dissolved hydrocarbons will generate a third stream such as stripping gas, liquid or solid adsorbents or sludge. The design of any system for the removal of dissolved hydrocarbons must allow for the handling and processing of these additional streams.

9.2 Dissolved hydrocarbons - Levels of dissolved hydrocarbons in water
9.2.
LEVELS OF DISSOLVED HYDROCARBONS IN WATER
Table 2.2 in Chapter 2 illustrates the solubility of a number of hydrocarbons in fresh water under atmospheric conditions. It can be seen that only the lighter aliphatic hydrocarbons and the aromatic hydrocarbons are appreciably soluble in water. In practice, for the following reasons, the actual solubility of hydrocarbons dissolved in waste waters will be significantly different from the solubility presented in Table 2.2.
0

Waste water is often saline and contains many contaminants which will affect the solubility of hydrocarbons.

At some stage in the process the waste water has usually been in close contact with a hydrocarbon phase. Water soluble hydrocarbons will still have an affinity for other hydrocarbons and the level of dissolved hydrocarbons in the water depend on how the hydrocarbons partition between the two phases.
The actual dissolved hydrocarbon concentration is a key parameter required for the design of equipment for the removal of dissolved hydrocarbons, yet is often not known at the design stage. A number of methods can be used to determine the probable dissolved hydrocarbon concentration. Water samples taken during well tests can be analysed to determine the dissolved hydrocarbon content. This can provide valuable information for subsequent design. The well test operating conditions should be clearly noted. From hydrocarbon and water analyses, computer simulation may be used to predict expected the levels of dissolved hydrocarbons. The accuracy of such prediction is typically in the order of f 30%. Samples of produced hydrocarbons and produced water can be used in laboratory trials to investigate the levels of dissolved hydrocarbons. While effects such as ageing will reduce the accuracy of laboratory tests, they can be used to give broad confirmation of other prediction methods. Methods for estimating the concentration of dissolved hydrocarbons in water are presented and discussed in Appendix J. KSLA have conducted a number of trials to investigate the solubility of hydrocarbons in water for a planned gaskondensate development. , The following results were found.
0

A relatively good correlation was found between predicted dissolved hydrocarbon levels and measured hydrocarbon levels, particularly when predicted results were compared against the levels of dissolved hydrocarbons from existing platforms.
The solubility of hydrocarbons in water was found to decrease with increasing water salinity.

0

No significant variation of the hydrocarbon solubility in water was measured when increasing the water pH from 4.5 to 7.0. No significant variation of the hydrocarbon solubility in water was measured when increasing the water temperature from 20°C to 50°C. The presence of methanol in the water phase was found to significantly increase the solubility of hydrocarbons in the water. The presence of corrosion inhibitor was found to significantly increase the apparent solubility of hydrocarbons in the water phase. However it is not sure whether the measured hydrocarbons were actually dissolved in the water or were present as an emulsion of very small dispersed hydrocarbons stabilised by the corrosion inhibitor.

0

These results are discussed in more detail in Appendix J.
e e

P u p 9-2-1

SlPM Deoilinx Morlrtrrl. EP 93-1315. Ruv I. 1. Nov 1993, File II(IIIIP = 901902,DOC

9.3 Dissolved hydrocarbons - Gas stripping
9.3. 9.3.1.

GAS STRIPPING

Introduction
Gas stripping of volatile compounds from water in a column is a relatively well established procedure. The basic design of a stripping process (using air as the stripping medium) is illustrated in Figure 9.3.1. Water and the stripping gas are counter-currently contacted in a packed column where the volatile components migrate from the water phase into the stripping gas. The most common stripping gases used are air, nitrogen and lean hydrocarbon gas. Steam stripping is discussed separately in section 9.4. The advantages and disadvantages of the various types of gas stripping mediums are summarised in Table 9.3.1.
H75117mP

r.-----

VOC'S

Feed

Air
I

Figure 9.3.1 Basic gas stripping configuration

It must be noted that stripping does not eliminate dissolved hydrocarbons, only transfers them from the water stream to the gas stream. A suitable route must be available to process or dispose of the stripping gas.

9.3.1 .l. Air stripping
The major advantage in the use of air as the stripping gas is the plentiful supply and low cost of air. However air stripping has a number of disadvantages related to the presence of oxygen in the air. The waste air from the stripping column contains oxygen and hydrocarbons and thus represents a potential explosion safety risk. The oxygen can promote biological fouling in the stripping column. The oxygen will promote corrosion, potentially requiring the use of more expensive construction materials for the column, internals and downstream water handling equipment. The volume of air required for air stripping is typically in the order of 30 to 100 times the volume of water to be treated (smVsm3). Excess air may be used to maintain the hydrocarbon concentration in the waste air below the lower explosion limit. The most convenient method of disposal of the waste air from the stripping process is using the air as feed to combustion equipment such as turbines or furnaces. If this is not possible, alternative disposal methods include activated carbon adsorption or incineration. Venting of the waste air stream is sometimes acceptable, however as benzene is often the major dissolved hydrocarbon component the health and environmental implications of the vented hydrocarbons must be carefully considered. In some cases it may be safer and simpler to deal with a contaminant in the water stream than transfer the contaminant to a gas stream. Due the presence of oxygen the waste air cannot usually use the normal vent system. The potential explosion hazard of the waste air stream must be carefully considered.

9.3.1.2.

Nitrogen stripping Nitrogen stripping operates in the same manner as air stripping, however does not incur the disadvantages introduced by the presence of oxygen. The major disadvantage of nitrogen stripping is the cost of generating nitrogen. The volume of nitrogen required is typically in the order of 30 times the volume of water to be treated and unless a suitable source of cheap nitrogen is readily available nitrogen stripping is not competitive with alternative stripping methods. The disposal of the waste nitrogen gas must also be considered. If venting of the waste gas is acceptable, normal vent lines may be used as nitrogen does not create an explosion hazard. However, the health and environmental implications of the vented gas must be carefully considered. If venting is not acceptable the waste gas must be cleaned by adsorption or incineration.

SlPM Duirilir~l:Moriir~tl, EP 9.?-1315, Rev 1. I . h'iiv 199.7. R l c

iiiiriir

= 9O.<STRIt'.OOC

P q e 9-3-1

9.3 Dissolved hydrocarbons - Gas stripping
9.3.1.3.

Lean hydrocarbon gas stripping
Stripping with hydrocarbon gas is possible if the aromatic content of the gas is suitably low. For example, to strip waste water containing 500 mg/l benzene to 10 mg/l, the maximum allowable concentration of benzene in the feed gas is in the order of 0.45 mole %. The stripping gas may actually increase the concentration of some soluble hydrocarbons such as methane in the water. This may not be acceptable and the water may require additional treatment to remove the new hydrocarbons. As with nitrogen stripping, the use of hydrocarbon gas as the stripping medium has the advantage of excluding oxygen from the process. The waste gas may be disposed by compression and export as product or used as fuel gas. These disposal routes may be cheaper than the disposal routes required by air or nitrogen stripping.

Advantages
1. Air is cheap and abundant.

Disadvantages
1. Explosion risk due to presence of oxygen. 2. Organic and biological fouling due to presence of oxygen. 3. Potential corrosion problems due to presence of oxygen. 4. Only transfers problem from water stream to air stream

Advantages
1. Eliminates explosion risk by excluding oxygen. 2, Can use normal vent system. 3. Eliminates oxygen associated corrosion and fouling.

Disadvantages
1. Cost of supplying nitrogen. 2. Only transfers problem from water stream to gas stream. Nitrogen may still need to be treated.

Advantages Eliminates all oxygen associated problems (explosion risk, fouling, corrosion). 2. Gas may be disposed as fuel gas or exported..
1.

Disadvantages

1. Gas may need compression for recovery. 2. Gas may have to be dried before it may be reused or exported. 3. May have less driving force for removing contaminants from water.

9.3.2.
9.3.2.1.

Performance variables
Hydrocarbon species Stripping is only suitable for the removal of volatile hydrocarbons which have an appreciable vapour pressure at the stripping conditions. The less volatile hydrocarbons will not be removed, including compounds such as the various glycols that may be present. Formic acid, acetic acid and methanol will not be effectively removed by gas stripping. Steam stripping which is discussed in section 9.4 may be used for the removal of less volatile components.

9.3.2.2.

Dispersed hydrocarbons Until recently, on the basis of previous investigations conducted by KSLA into the stripping of dispersed water from condensate (1982 - 1985, 3.02.2.d to h), it has been assumed that the removal of dispersed droplets from a liquid phase by gas stripping occurred by the dispersed hydrocarbons first dissolving into, and then being stripped from, the water phase.

PUXC 9-3-2

SIPM Droiliiiji M(oiic(i/.EP 93-I.?/.(.Rrv 1.1, Nov 1993. File iiomr = 903STRIP.DOC

9.3 Dissolved hydrocarbons - Gas stripping
This two step mechanism was assumed to be required as it was considered that direct contact between the dispersed water and the gas bubbles would be too infrequent and too short to make any significant contribution to the stripping process. This mechanism was also assumed to apply to the stripping of dispersed hydrocarbons from water. However, recent trials at KSLA investigating the stripping of dispersed n-heptane, toluene and Shellsol-K from water (Ref. 3.02.2.b, 3.02.2.c) showed that, provided the hydrocarbons were sufficiently volatile, the dispersed hydrocarbons could be directly removed from water by a stripping process, contradicting the previous assumptions. The dissolution model cannot apply to these hydrocarbons as they have a very low solubility in water, thus the mass transfer must take place directly into the gas phase. However, the trial also highlighted a number of shortcomings encountered when stripping dispersed hydrocarbons from water. The ability to strip a dispersed hydrocarbon is related to its volatility. Non-volatile hydrocarbons will not be removed or only removed at a low rate. Packed columns are sensitive to fouling. The presence of dispersed hydrocarbons and solids may accelerate such fouling. From these results the following conclusions can be drawn; The results suggest that volatile dispersed hydrocarbons can be directly stripped from water without having to first dissolve into the water phase. This finding contradicts previously held assumptions on mass transfer mechanisms for dispersed droplets and will need to be investigated further. However the trials also showed that non-volatile hydrocarbons will not be removed by stripping and that the stripping of even the volatile hydrocarbons may not be very efficient. In addition, the presence of dispersed hydrocarbons in the feed stream may lead to operating problems such as fouling within the column. On the basis of these results it is recommended that, in general, stripping columns should not be designed for the removal of dispersed hydrocarbons as non-volatile hydrocarbons will not be removed, the mass transfer mechanisms are not sufficiently defined for accurate design and operating problems may be experienced in the column. Thus dispersed hydrocarbons (and suspended solids) should be removed by conventional deoiling equipment upstream of the stripping column. The stripping column can then be reliably designed for the removal of dissolved hydrocarbons using well proven design methods. An exception could be the removal of a relatively clean, volatile dispersed phase as may be found in an gaskondensate operation. However, laboratory or pilot scale trials would be required to obtain sufficient data to be confident of the sizing and performance of such a column.

9.3.2.3.Temperature
The performance of the stripping process will be affected by the operating temperature. The temperature influences a number of variables including: Mass transfer rate: Higher operating temperatures will improve the rate of mass transfer of hydrocarbons from the water to the gas phase. Vapour pressure: The vapour pressure of volatile hydrocarbons increases. Viscosity: Higher operating temperatures will lower the water viscosity, improving the mixing and mass transfer in the column. Saturation of stripping gas: The operating temperature may have an impact on the quantity of hydrocarbons that can be absorbed by the gas.

9 . 3 . 3 .
9.3.3.1.

Installation/Configuration

Process location
To minimise the size of the gas stripping equipment it is desirable to ensure the majority of dispersed hydrocarbons are removed from the water stream by upstream equipment. Thus gas stripping columns are usually located downstream of water treatment facilities designed for the removal of the majority of

9.3 Dissolved hydrocarbons - Gas stripping
dispersed hydrocarbons such as hydrocyclones, centrifuges, flocculation/flotation or filtration processes.

9.3.3.2. Size and cost
Appendix K gives a comparison of the size and cost of a range of equipment suitable for the removal of dissolved hydrocarbons.

9.3.4.

Design guidelines
The basic mass transfer theory governing the design of air and stream strippers is covered in detail in a range of standard chemical engineering textbooks. Additional information can be found in the references listed in the Bibliography. The physical parameters to be evaluated during the design stage are tower diameter, gas-to-water ratio, and packing type, size, depth and pressure drop. These parameters are interrelated. The number of transfer units, gas-to-water ratio and tower height influence removal efficiency and effluent quality. The gas-to-water ratio is dependent on the stripping factor and Henry's constant. Initial design calculations should be based on the compound to be stripped which has the highest concentration and the lowest Henry's constant. The packing size and the gas-to-water ratio affect the gas pressure drop. The practical limit for the gasto-water ratio is related to the pressure drop through the tower with the pressure drop rising as the gasto-water ratio increases. When using air, an air-to-water ratio of 15:l is considered to be low, ratios of 22:l to 30:l are better while a ratio of 50:l is considered high. Typical pressure drops are 0.8 to 4.2 cm of water column per meter of packing.

Pap2 9-3-4

SlPM Droiliir~ Mmriol. EP 93-131.5, Rev 1. I . Nov 1993, File ncrine = 903STRIP.DOC

9.4 Dissolved hydrocarbons - Steam stripping
9.4. 9.4.1. STEAM STRIPPING Introduction
Steam stripping is similar to gas stripping in that the volatile organic compounds in the water are transferred into a gas phase. In the case of steam stripping the gas phase is steam. The following section discusses the use of stream stripping, however the user is also referred to section 9.3 for additional information on stripping processes. There is also extensive refinery experience in the use of steam stripping for the removal of hydrogen sulphide and ammonia from waste waters. The advantages and disadvantages of steam stripping are examined in more detail in the following discussions and are summarised in Table 9.4.1. Steam stripping has the advantage of operating at a higher temperature than gas stripping. The higher temperature allows the removal of the less volatile hydrocarbons. Vacuum pumps may also be used to lower the pressure in the column, lowering the boiling temperature and assisting the removal of nonvolatile hydrocarbons. Operating at a lower temperature under vacuum may also allow sources of low grade heat to be used in the generation of the steam. The use of steam ensures that oxygen is excluded from the process, minimising explosion risks and oxygen supported fouling and corrosion.
A preheater may be used to recover energy from the discharged water stream. Consideration should be given to the possible impact of the elevated temperature of the discharged water stream on the environment.

The overhead stream from the stripper will consist of steam and hydrocarbons. This stream can be condensed, forming liquid water and hydrocarbon phases which can be separated. The hydrocarbon saturated water can be returned to the column and the separated hydrocarbons recycled to an appropriate part of the process or spiked into an export stream. Condensing of the overheads stream minimises the emissions from the stripping process apart from a relatively small vent flow of noncondensable gases. 9.4.1.1. Closed steam stripping

A closed steam stripping system is illustrated in Figure 9.4.1. A reboiler is used to evaporate a percentage of the product water stream which then rises against the down-coming water stream, stripping volatile hydrocarbons from the water.
The potential disadvantage of closed steam stripping is precipitation and fouling in the reboiler, particularly in the presence of saline waste waters . 9.4.1.2.

VaDour
Prehea ter

-

r

Condenser

I

Water reflux

Cooling water

Reboiler
H75117/9P

Open steam stripping

I

An open steam stripping system is similar to the closed steam svstem illustrated in Fiaure 9.4.1. However in place of a reboiler, dGect steam injection is used in the column. This eliminates the potential problems of boiler fouling and open steam stripping may be particularly attractive if a source of low grade steam is available.

Figure 9.4.1 Basic steam stripping configuration

+Treated water

9.4.2.
9.4.2.1.

Performance variables
Dispersed hydrocarbons Section 9.3.2.2 presents a range of arguments against the use of gas stripping for the removal of dispersed hydrocarbons. These arguments also apply to steam stripping, through the following factors will improve the removal of dispersed hydrocarbons in a steam stripping process. Higher operating temperatures will improve mass transfer rates. More of the heavier aliphatic compounds will be removed at the higher temperature.

9.4 Dissolved hydrocarbons - Steam stripping
However, in general it is recommended that stripping columns are not designed for the removal of both dispersed and dissolved hydrocarbons.

9.4.3.

Installation/Configuration

9.4.3.1. Process location
To minimise the size of the steam stripping equipment it is desirable to ensure the majority of dispersed hydrocarbons are removed from the water stream. Thus steam stripping columns are usually located downstream of water treatment facilities designed for the removal of the majority of dispersed hydrocarbons such as hydrocyclones, centrifuges, flocculation/flotation or filtration processes.

9.4.3.2. Size and cost
Appendix K gives a comparison of the size and cost of a range of equipment suitable for the removal of dissolved hydrocarbons.

9.4.4.

Design guidelines
See related information on gas stripping (section 9.3.4.).

Advantages

Disadvantages Energy cost. Potential scaling in column and/or reboiler for closed steam stripping. Cost of losing treated boiler water in open steam stripping systems.

1. Overheads are condensed therefore potential
2.

3.
4.

5.
6.

vapour emissions are low. Can remove more non-volatile hydrocarbons by operating at higher temperatures or at sub atmospheric pressures. Economical if sources of waste heat are readily available. Improved mass transfer at elevated temperatures. Oxygen is excluded, minirnising organic and biological fouling and the need for expensive materials for corrosion resistance. Hydrocarbonsare recovered and returnedto the

P U ~ 9-4-2 C

SlPM DeoiI;il# Monuol. EP 93-1315. Rev 1.1. Nov 1993, File name = 904STfXM.DOC

9.5 Dissolved hydrocarbons - Biological treatment
9.5.
9.5.1.
BIOLOGICAL TREATMENT Introduction
Biological treatment systems use bacterial metabolism to convert biodegradable components in waste water into energy to sustain metabolism and by-products such as water, carbon dioxide, methane and biomass. The scope of biological treatment is broad and cannot be covered in detail in this manual. The following discussions present a brief introduction to biological treatment processes, additional information can be readily obtained from the references given in the Bibliography or from a wide range of commercially available references and text books. Biological treatment systems have been widely used for the treatment of waste waters from onshore refining and chemical industries, however are not often applied to the waste waters from E & P operations, particularly produced waters. Typical produced waters present some difficulties for biological treatment as they are often highly saline, may contain a mix of chemicals relatively toxic to micro-organisms and may have elevated temperatures. In addition, the size and weight of biological treatment systems has generally excluded their use from offshore installations, particularly for large produced water flow rates. However more compact and efficient bioreactor designs are being developed and a tightening of effluent quality standards may result in a wider application of biological treatment in E & P operations. Biological treatment processes can be divided into aerobic and anaerobic systems. In aerobic systems micro-organisms consume the organic components in the waste water in the presence of oxygen or air to produce cell growth and end products of carbon dioxide and water. Aerobic systems produce a high quality effluent, but also produce a relatively large quantity of biomass which is typically separated as a sludge. In anaerobic systems, the organic components in the waste water are biologically oxidised in the absence of air, yielding methane and carbon dioxide. The production of methane can be sometimes turned to advantage by using the methane as a source of energy. Anaerobic systems also produce less sludge and require less nutrients than aerobic systems and do not require energy to be expended in aeration. Because the biological reaction is not limited by the need to transfer oxygen into the system, anaerobic systems tend to require less residence time and can thus be more compact than aerobic systems. The advantages of both aerobic and anaerobic processes can be combined by using a primary anaerobic treatment stage for removal of the majority of the contaminants (with a lower sludge production), followed by an aerobic treatment stage for a higher quality effluent. Biological treatment systems can also be broadly categorised as suspended growth or attached growth systems. In suspended growth systems the micro-organisms move freely through the waste water, often supported by mechanical or hydraulic agitation. In attached growth systems the micro-organisms become attached to a suitable medium and the waste water stream contacts the combined medium/micro-organism system. Table 9.5.1 presents a summary of some of the available biological treatment systems and their potential range of application. All biological processes produce a waste sludge stream. The design of a biological process system must consider the requirements for the further treatment or disposal of the produced sludge.

9.5.2.

Aerobic processes
The following discussions present some of the common aerobic biological treatment systems. Aerobic systems produce a high quality effluent, but also produce a relatively large quantity of biomass in the form of sludge. Modifications to the aerobic process can minimise sludge production by encouraging the further metabolism of produced cell material by endogenous respiration. Up to 80% of the sludge can be oxidised but 20% is stable under aerobic treatment conditions and must be processed further. The aeration provided to enhance the aerobic treatment processes will have a stripping effect on the waste water. Volatile compounds such as aromatic hydrocarbons may be stripped from the water by the aeration rather than biologically degraded. The potential HSE implications of passing such contaminants into the atmosphere must be carefully considered.

SlPM Deiiiliitfi M ~ i i i i i ~ EP ~ l 9.1-131.5, , Rev 1.1. N o v 1993. File iiiiiiii' = 9OSRIO.DOC

Puxe 9-5-1

9.5 Dissolved hydrocarbons - Biological treatment
9.5.2.1. Activated sludge The activated sludge process is a continuous flow, aerobic process. Figure 9.5.1 illustrates a basic activated sludge process. The process is characterised by a suspension of micro-organisms which is mixed with the incoming waste stream in the aeration system. The organic contaminants in the feed stream are biologically oxidised, resulting in the growth of micro-organisms and the formation of waste products. After aeration and oxidation the biomass is separated from the treated water in a clarifier, resulting in a treated effluent water stream and a sludge stream. A proportion of the sludge is recycled to the start of the process to maintain the biological activity in the process.
H75117/14P

Aeration effluent Waste sludge

Figure 9.5.1 Basic activated sludge process

A range of modifications to this basic process can be considered such as contact stabilisation, extended aeration, step aeration and oxygen activated sludge. Each modification has characteristics which may suit different process requirements such as minimising complexity, minimising sludge production or maximising removal of contaminants. 9.5.2.2.

Fluidised beds

sludge process as the biomass is attached to the carrier particles and effectively has a long residence time in the reactor. This allows the biomass to be decomposed rather than just being produced as sludge.

Nutrients

Water

9.5.2.3.

Aerated lagoons An aerated lagoon is a basin, typically 2.5 to 5.0 m in depth covering a large area that is aerated by diffusion or surface agitation. In an aerobic lagoon the system must be well mixed to maintain aerated conditions throughout. In a facultative lagoon, only the surface of the lagoon is aerated and some solids settle on the bottom of the lagoon where they decompose through anaerobic processes.

9.5.2.4.

Trickling filters The trickling filter is an attached growth system where the waste water is passed (trickled) over microorganisms attached to a solid media. As the waste stream passes over the media the organics are oxidised by the attached micro-organisms. Historically the support media has been rock, however alternative media such as plastic and wood are now commonly used which can handle a higher water loading and a greater packing depth. Due to the short residence time, tricking filters cannot remove as much BOD as the activated sludge process, however, they are simpler to operate and can pre-treat high strength waste waters efficiently. However they may also be severely affected by rapid variations in the feed stream characteristics as there will be little or no dilution of the feed stream.

9.5.2.5.

Rotating biological contactors In rotating biological contactors the micro-organisms attach to a disc shaped support which rotates through a basin of waste water. The rotation of the discs contacts the biomass with the organic material in the waste water and then with the atmosphere above the water for oxygen adsorption.

P U ~9-5-2 C

SlPM D e o j h g Mrrriirol, EP 93-1315, Rev 1.1. Nov 1993. File ncrme = 905BIO.DOC

9.5 Dissolved hydrocarbons - Biological treatment
9.5.2.6. Use of activated carbon Some activated sludge processes use activated carbon powder to assist the water treatment. The activated carbon can remove remaining contaminants that are not biologically degraded. The carbon can then be removed from the system as part of the sludge stream.

9.5.3.

Anaerobic processes
Anaerobic treatment converts soluble organic materials to methane, carbon dioxide and energy to support cell growth in the absence of gaseous oxygen. Anaerobic processes produce less sludge than aerobic processes with 80 to 95% of the biodegradable contaminants being converted to carbon dioxide and methane. Anaerobic process are typically used for highly contaminated waste waters containing at least 1,500 mg/l BOD and can handle a COD of 10,000 mg/l or higher. The anaerobic reaction consists of two stages. Conversion of soluble organic compounds to volatile fatty acids (mostly acetic acid) Digestion of the volatile fatty acids resulting in methane and carbon dioxide. The methane forming micro-organisms involved in the second stage are more sensitive to environmental conditions such as pH, nutrients and temperature than the acid forming micro-organisms in the first stage. The methane forming organisms also have a lower growth rate and will take longer to recover from inhibition or shock loading.

9.5.3.1.

Suspended systems
Suspended anaerobic conditions can be maintained in lagoons or vessels. Anaerobic lagoons can be used where close control of the process and a high degree of treatment is not required. The anaerobic contact process is illustrated in Figure 9.5.3. This process is similar to the activated sludge system combing a reactor and a settling tank with some sludge recycled. Figure 9.5.4 illustrates an up-flow blanket process where the biomass is suspended by the waste water flow. Solids concentration is controlled by periodic discharge of biomass while water clarity is maintained by setting the up-flow velocity lower than the settling velocity of the biomass blanket.

Reactor

ir

Underflow

H75117/12P

9.5.3.2.

Attached systems Because of the problems that may be experienced in clarifying suspended growth systems, attached growth systems are often utilised for treatment of wastes which are free from suspended solids. The micro-organisms attach to a fixed media, contacting the water stream. Up-flow and down-flow configurations can be used. Fluidised beds may also be used with the microorganisms attached to a fluidised media bed. This potentially allows both a higher loading rate and more surface area for growth of micro-organisms, resulting in a smaller reactor. A disadvantage is the energy required to fluidise the bed. An additional consideration is a need to be able to remove excess biomass from the system and to treat or recycle this excess.

_ M M M N

Gas collection

Sludge blanket

f

Figure 9.5.4 Anaerobic upflow blanket

Feed

H75117/13P

9.5 Dissolved hydrocarbons - Biological treatment
9.5.4.
9.5.4.1.

Performance variables

Process environment
In order to support the growth of the micro-organisms the waste water must provide a suitable and stable process environment. Typical environmental conditions for biological systems are a pH of between 6 and 9, sufficient nutrients for growth, c 2:l variation in organics loading, < 125 mg/l suspended solids (TSS), 4 5 mg/l dispersed hydrocarbons, < 1 mg/l (typically) of heavy metals, and a temperature between 5 and 40°C.Higher temperatures could possibly be accommodated with more thermophilic micro-organisms. Biological treatment systems have been effectively used for the treatment of a wide range of contaminants in relatively fresh water. However production waters from E & P operations are often very saline which can be a more difficult environment for the growth of suitable micro-organisms.

9.5.4.2.

Toxicity The micro-organisms present in a biological process are capable of adapting to a wide range of process conditions, allowing the processing of even relatively toxic contaminants. However, it is important to ensure that the process environment is maintained relatively constant. The environmental shocks from a rapid change of any parameter may result in a significant drop in biological activity until the system can adjust and recover. The system should thus be protected from any sudden changes in the process environment such as changes in temperature, pH, salinity or organic composition.

9.5.4.3.

Dispersed hydrocarbons The micro-organisms in a bioreactor live in the water phase and will not be able to effectively attack dispersed hydrocarbons. Where the biomass is attached to a substrate, dispersed hydrocarbons may result in fouling of the biomass support. It is recommended that the majority of dispersed hydrocarbons are removed upstream of the biological reactor.

9.5.5. 9.5.5.1.

Installation/Configuration
Process location Biological treatment systems should be located as a tertiary water treatment stage. This ensures the majority of dispersed hydrocarbons are removed upstream of the biological treatment systems and also helps ensure a more stable, consistent feed steam, protecting the system from surges or high loadings of contaminants.

9.5.5.2.

Size and cost
Appendix K gives a comparison of the size and cost of a range of equipment suitable for the removal of dissolved hydrocarbons, including a fluidised bed aerobic biological treatment system.
0

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SIPM Deoiliitg Mnittrol, EP 93-1315. Rev 1.1, Nov 1993. File niiine = YO5BIO.DOC

9.5 Dissolved hydrocarbons - Biological treatment
Table 9.5.1 Biological treatment processes

Treatment process

Aerobic
Activated sludge Extended aeration Rotating biological contactor Trickling filter Aerated lagoon (aerobic) Aerated lagoon (facultative) Anaerobic Anaerobic reactor Anaerobic pond Facultative pond

Retention time (days) 1.16 - 0.33
0.5

Depth
(m)

BOD5 in feed (mgll)

'emoval (%)

BODS

Conditions

3-5 3-5 N.A.

2000-3000 100 - 3,000
3000-4000 N.A. N.A.
:

85 - 95 Prevent sludge bulking 85 - 95 FIM c 0.2 80 - 95 Loading 1.5 to 8 Ib B0DRt2.d

- 1.0

100 - 3,000

N.A. N.A.
0.5 - 3.0

50 - 500
500 - 3,000
50 - 750

4-9
2.5 - 5 2.5 - 5

50 - 60 Loading 0.1 to 0.5 Ib BODm3.d
50 - 70 Well mixed

3-10

0.5 BOD ir feed 50 - 100

50 - 250

80 - 95 Surface mixing

0.5- 30

N.A. 2.5

5000-12000 1500-1 OOOC
c 25

70 - 95 Loading 0.1 to 0.95Ib
6ODIfP.d BOD/acre.d 70 - 95 Loading20 to 50 Ib B0Dlacre.d; algae 10-50 mad LT., Chemical Eng, Sept 2, 1985

5 - 50

-5

500 - 2,000 50 - 80 Loading 250 to 4,000Ib
50 - 250

7 - 50

1-2.5

c 25

1. Source: Waste water tre ment. Eckenfelder JI N.W., Patoc ka, J, Watkir 2. BOD Biological Oxygen Demand, F/M food to micro-organismratio, N.A. 1

-

SIPM Droilrn~ Monucil. EP 93.1315, Rev 1.1, Nirv 1993. File

iiiiiiir

= 9051110 DOC

~-

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9.5 Dissolved hvdrocarbons - Bioloaical treatment

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PUK" 9 - 5 6

SlPM Duoiliitl: Mniiiccil, EP 93-1315, Rev 1.1, Nov 1993. File nome = 905BIO.DOC

9.6 Dissolved hydrocarbons - Activated carbon

..
9.6.1.

ACTIVATED CARBON Introduction
Activated carbon is manufactured from organic materials such as coal, wood, or coconut shells. The raw material is activated by treatment at an elevated temperature, resulting in a highly porous structure with a high internal surface area. The activated carbon is packaged in a similar manner to filtration equipment, either as a deep bed or as a cartridge and the contaminated water passes through the carbon bed. Contaminants in the waste water are adsorbed onto the carbon surface due to the attractive forces between the carbon surface and the contaminants. Contaminants with a relatively low solubility in water such as aromatic hydrocarbons will be readily adsorbed as they will tend to have a greater affinity for the carbon surface than for the water phase. More water soluble contaminants such as fatty acids and alcohols will not be as efficiently adsorbed as they will have a higher affinity for the water phase. Eventually all the adsorbing sites in the carbon bed will be saturated with contaminants, leading to a breakthrough of the contaminants into the outlet water stream. Once bed saturation is reached, the carbon must be either regenerated or disposed. Regeneration requires heating to volatilise and pyrolise the adsorbed contaminants, thus recovering the adsorption sites. Generally, about 10% of the carbon is destroyed during the regeneration process while the remaining carbon is regenerated to about 90-95% of its original capacity. Fresh activated carbon must be added to compensate for these losses. The contaminants removed from the carbon will be present in the waste gases from the regeneration process and a regeneration scheme must consider the additional treatment that may be required to safely dispose of the waste gases. If steam is used for regeneration a contaminated water stream will be produced. Disposal of saturated carbon can be through landfill or incineration. However consideration must be given to the HSE impact of any disposal methods with respect to the nature of the contaminants trapped in the carbon. Activated carbon will remove a wide range of contaminants including aromatic hydrocarbons and phenols. However, the levels of fatty acids and heavy metals will not be significantly reduced.

9.6.2.
9.6.2.1.

Performance variables
Temperature and p H Activated carbon adsorption is normally conducted at temperatures lower than below 95°C. As temperatures increase, the volatility of the compounds to be adsorbed increases, reducing their affinity for the absorption sites on the surfaces of the carbon. Adsorption of contaminants can also be enhanced or reduced by pH. In general a neutral or slightly acidic pH is most effective, however it is often found that acidic compounds are more effectively adsorbed in the presence of a low pH while bases are more effectively adsorbed in the presence of a high PH.

9.6.2.2.

Dispersed hydrocarbons and solids Dispersed hydrocarbons will tend to coat and block the pores of the activated carbon, reducing the capacity of the carbon bed. Solids will be filtered from the water by the carbon bed, however the system is not designed to act as a filter and the presence of solids will shorten the active life of the bed. Thus it is recommended that dispersed hydrocarbons and solids are removed upstream of activated cahon systems.

9.6.2.3.

Adsorption isotherm A liquid phase adsorption isotherm test is the basic preliminary evaluation tool to determine the ability of activated carbon to adsorb a given contaminant. The adsorption isotherm is determined through a batch test in which a fixed quantity of water sample is contacted with varying quantities of activated carbon. Results of an adsorption isotherm are usually expressed in terms of the capacity of the carbon for a given contaminant at a specified equilibrium concentration. A typical adsorption isotherm is illustrated in Figure 9.6.1. The isotherm curve will approach a straight line on a logarithmic plot and is mathematically described by the following expression known as the Freundlich equation (Eq. 9.6.1).

SIPM Droilink

Miiriiiiil.

EP 93- 1315. Rrv I . I . NIIV1993. Filr iiiiiiic = 9ObCARI~N.DOC

Puge 9-6-1

9.6 Dissolved hydrocarbons - Activated carbon

-=kxC m where:

X

1 -

n

Eq. 9.6.1

x

m k C

= mass of contaminant adsorbed = mass of activated carbon = constant, related to the absorption of the contaminant = concentration of unadsorbed contaminant left in solution = sensitivity of the adsorption to contaminant concentration

Table 9.6.1 gives some typical Freundlich isotherm constants for single component adsorption from water. It can be seen that the water soluble alcohols and organic acids have a relatively low value of k and are thus poorly adsorbed compared to the aromatics and substituted aromatics.

Contaminant

Intercept k (mqlq)

Slope (lln)

Aniline Benzene sulphonic acid Benzoic acid Butanol Butyric acid Chlorobenzene Nitrobenzene Phenol Trinitrotoluene Toluene
1.
I

25 7 7 4.4 3 . 1 40 82 24 270 30

Source: “Remove organics by activated carbon adsorption”, Mark H Stenzel, Calgon Carbon Cop., Chemical Enqineering Progress, April 1993, pg 36 - 43

I

0.322 0.169 0.237 0.445 0.533 0.406 0.237 0.271 0 . 11 1 0.729

The adsorption isotherm can be used as a preliminary guide to determine whether a contaminant is likely to be successfully adsorbed by activated carbon, and provide an initial estimate of the quantity of carbon required. However, the isotherm does not provide sufficient information for detailed design. Dynamic testing or pilot trials are normally required to determine the practical performance of an activated carbon system when faced with complex mixtures of contaminants in production waters. This will evaluate factors such as the contact time required to achieve equilibrium and the shape of the contaminant breakthrough curve as the carbon bed becomes saturated.

9 . 6 . 3 .

Insta Ilat ion/Conf igurat ion

9.6.3.1. Process location
The main operating cost associated with activated carbon systems is the replacement or regeneration of the carbon once it is saturated. Thus activated carbon systems should be placed in a location where the life of the carbon will be maximised. In addition, the levels of dispersed hydrocarbons and suspended solids in the water should be low. These requirements dictate that an activated carbon system should be used as a tertiary treatment stage at the end of the water treatment system.

9.6.3.2. Biological reactors
Activated carbon may be used to assist biological reactors. The addition of activated carbon to a biological treatment process may absorb the non-biodegradable contaminants from the water. The activated carbon is then separated in the settling vessel and removed with the sludge. In an activated sludge system some of the carbon will be recycled to the bioreactor where it can act as a substrate supporting a film of micro-organisms.
0

9.6 Dissolved hydrocarbons - Activated carbon

1000

1

0.01

0.1

1

10

-

Residual concentration mgA rn-Xylene

-

Toluene

- - Benzene

Figure 9.6.1 Single component activated carbon adsorption isotherms Illustrative only Not to be used for design

SIPM Droiliiiji

M~iiiiial. EP

93-1315. Rrv I . 1. Nov 1993. File ii~iiiir = 906CARRN.DOC

Puxc 9-6-3

9.6 Dissolved hvdrocarbons - Activated carbon

Puxe 9-6-4

SIPM Deoilirig M m i i i i l , EP 93-1315, Rev 1.1. NIJV1993, File name = 906CARBN.DOC

9.7 Dissolved hydrocarbons - Solvent extraction
9.7. 9.7.1. SOLVENT EXTRACTION Introduction
Solvent extraction, or liquid-liquid extraction, may be applied to the clean-up of water containing both dissolved and dispersed hydrocarbons. Solvent extraction is a mass transfer process where the feed, containing dissolved and dispersed hydrocarbons, is contacted with a suitable immiscible solvent. Correct solvent selection will allow dissolved hydrocarbons (and possibly dispersed hydrocarbons) to be transferred from the water stream to the solvent. The solvent and water phases are then separated, producing two product streams, the extract, which is the solvent stream containing the extracted hydrocarbons and the raffinate, which is the clean water stream. After extraction the solvent must be either regenerated or disposed. Regeneration usually involves a distillation of the solvent to remove the contaminants. The contaminants must then be disposed in an appropriate manner. Alternatively the solvent may be disposed in a suitable product stream. An example is the use of kerosene as an extraction solvent. This could either be regenerated and recycled for extraction, or disposed into a crude oil export stream where it will effectively recover some of its cost by being sold as crude oil. Although there are no known E & P operations using solvent extraction as a method for removing hydrocarbons from waste water, the technology and unit operations involved are relatively well defined. Additional information can be readily found in standard chemical engineering texts or the references in the Bibliography.

9.7.2.

Co-current extraction
Conventional solvent extraction facilities use mixer/settlers or counter current contacting columns to achieve the required extraction. A more compact alternative is the use of a pseudo counter-current system as illustrated in Figure 9.7.1. This system consists of two or more co-current contact stages, each stage comprising a static mixer for co-current contacting and a hydrocyclone for separation of the produced phases. This process is essentially the same as the mixedsettler process, however the equipment is considerably more compact.

H75117110P

Coalescer /

Rich solvent

Lean solvent

I

Figure 9.7.1 Pseudo counter-current solvent extraction

Treated water

I

Key criteria determining the practicality of this system are the number of stages needed to achieve the required quality in the effluent water and the ability of the hydrocyclone to achieve a sufficiently high separation efficiency to remove the dispersed solvent from the water. This extraction system is undergoing pilot plant studies at KSLA. The estimated size and weight of such a system is compared with other processes for the removal of dissolved hydrocarbons in Appendix K.

SlPM Deoiliriji Marirrol. EP 93-1315, Rev 1.1. Nov 199.7. File

riirrirr

= 907EXTRT.DOC

Puge 9-7-I

9.7 Dissolved hydrocarbons - Solvent extraction

THIS PAGE HAS BEEN INTENTIONALLY LEFT BLANK

Pose 9-7-2

SlPM Deoilrnl: M U I I I ~ t ,P 93-1315, Rev 1.1. Nov 1993, File name = 907EXTRT DOC

IO. New technology

10.1.

GENERAL
Due to the increased emphasis on environmental protection at both community and industry level, a range of new technologies are under development for the removal of contaminants from waste water streams. The following discussions present some of the promising technologies that are currently under development, either within Shell or by independent parties. Although these technologies are generally not yet commercially feasible or available at the present, they are presented to increase the general awareness of potential new developments which may in turn provide an impetus for their further development.

10.2.

OZONWULTRAVIOLET
Ozone/ultraviolet treatment is a chemical oxidation process. Ozone is generated by passing air or oxygen through a high voltage corona discharge. The ozone yield varies from 1 - 2% when using air to 3 - 5% when using oxygen. The ozone containing air or oxygen stream is then injected into the waste water st ream. By exposing the ozone containing water to ultraviolet light, oxygen radicals are generated that will chemically attack and break down the organic components of the water, producing carbon dioxide and water. The technology is suited to relatively low levels of contamination (less than 10 mg/l organics). It has the advantages of being relatively compact, achieving a reduction of organic contaminants to very low levels and does not produce any additional waste streams. This could potentially be considered as a tertiary treatment stage for the removal of relatively low levels of dissolved organic materials.

10.3.

ADSORPTION ON MODIFIED ZEOLITES
Zeolites are commercially available minerals consisting mainly of hydrous silicates of calcium, sodium and aluminium exchangeable cations. Modified zeolites are created by altering the natural chemistry of zeolites with ammonium ions displacing other cations. Zeolites can potentially be used as an adsorbent for the removal of dissolved hydrocarbons from water. Modification of the zeolites makes them more sefective for dissolved aromatic compounds and test work indicates that the modified zeolites would operate as a satisfactory adsorbent for produced waters. However at this stage the technology is at the laboratory stage of investigation and additional work would be required to investigate the potential commercial application of the process.

10.4.

MEMBRANE LIKE MATERIAL
Membrane like material (MLM) is a compound formed from a solvent, water and an extract of bitumen. The MLM arranges itself as a film (which acts as a membrane) separating hydrocarbons and water into two distinct phases. The membrane will partition solvent and oily components from aqueous mixtures, capture and remove oily materials from solid surfaces and reduce the residual amounts of partly water soluble solvents in water. The MLM has potential application in the clean up of oily waters and oil contaminated solids.

10.5.

PERVAPORATION
Pervaporation is a distillation process combined with a membrane separation. In a distillation, mixtures are separated by exploiting the different volatility of the components. Membranes separate mixtures by exploiting the different permeability of the components through the membrane. These separation processes can be combined in series by using a membrane at the vapour liquid interface. The composition of the vapour will thus be dependent on both the vapour-liquid equilibrium and the membrane permeability. Pervaporation can be used for the removal of dissolved volatile hydrocarbons from water. It can be thought of as vacuum distillation with the packed stripping column replaced by a membrane. A vacuum pump on the permeate side ensures a concentration gradient across the membrane, drawing both water

10. New technology
and hydrocarbons from the waste water stream. A membrane is selected which is more permeable to hydrocarbons than water and a separation is achieved as the hydrocarbons evaporate from the water under the effect of the vacuum. By replacing a packed column with a membrane package pervaporation has the potential to offer weight and space savings. However issues such as membrane life and fouling must also be considered. The pervaporation process may also be applied for the purification of glycol in glycol regeneration systems. Appendix K provides a comparison of a potential pervaporation system with other methods for the removal of dissolved hydrocarbons. KSLA is conducting further investigations into pervaporation.

10.6.

MEMBRANES FOR DISSOLVED HYDROCARBONS
Non-porous membranes have the potential to separate dissolved hydrocarbons from water on the basis of different rates of permeability through the membrane. The SDI Extran membrane discussed in Appendix L has been shown to have some ability to separate dissolved hydrocarbons from water, through this may be partially assisted by the presence and concentration of dispersed hydrocarbons in the recycling concentrate. Although membranes are considered a very promising development, additional work is required to improve the performance of membranes in the field with respect to membrane life, fouling and cleaning. At this stage, none of the commercially available membranes can be considered at a suitable stage of development for the removal of dissolved hydrocarbons.

.

.

Appendix A - Emulsification and coalescence

. . .................,....

A.l.

Introduction
By definition, an emulsion is simply a dispersion of one immiscible liquid in another. When energy is input into such a dispersion it has two contrasting effects. Some of the energy will assist the emulsion, providing sufficient energy to the dispersed phase to support the dispersed droplets, overcoming their natural tendency to coalesce. However, at the same time, some of the energy input into the system will also increase the chances of dispersed droplets colliding and coalescing. For a given level of energy input into a system, there will be a maximum droplet size which is related to the dynamic equilibrium between the forces for dispersion and coalescence. For additional information on the concepts presented in this Appendix the user is referred to the following reference (Ref.l.08.1 .d); “Flow induced coalescence in chemical dehydration”, F. Meijs, W.J. van Beest, KSEPL report RKGR.0006.69, EP 40068, Jan 69

A.l.l

Mixing intensity
The mixing energy is defined as the work performed on a fluid per unit mass per unit time as expressed in equation A.l.

Eq. A.l

where:

E

= mixing intensity, the work performed on the fluid per unit mass per unit time (m*/s3) = pressure drop over a system (Pa) = retention time of the fluid in the system (seconds) = density of the continuous phase (kg/m3)

Ap
t pc

A.1.2

Prediction of droplet size
Various experimental and theoretical studies have been performed to relate droplet size to the input of energy to a system containing two liquid phases. A relationship between the maximum stable droplet size and mixing intensity was developed by Hinze of the form;

Eq. A.2

where:

,,, d
E
( r

= maximum stable droplet size (microns)

= mixing intensity ( m W ) = interfacial surface tension (N/m)

It must be noted that this equation calculates the maximum stable droplet size that can be expected in an unstable emulsion that is not stabilised by the presence of emulsifying agents. In practice, many of the emulsions encountered in oil and gas processing are stabilised and thus the maximum droplet size will be smaller than that predicted by the Hinze equation. Also, the Hinze equation predicts the maximum droplet size, the averaae droplet size will be smaller.
Similarly, this relationship is only valid for liquid-liquid systems. The relationship expressed in equation A.2 will not be valid in a system containing free gas or where gas break-out may occur as the presence of gas will alter the manner in which energy is absorbed by the system.

Appendix A - Emulsification and coalescence
From inspection of equations A.l and A.2, the following conclusions can be drawn. The greater the pressure drop per unit time, the smaller the maximum droplet size that will be generated. Thus a pressure drop experienced over a short time (e.g. over a control valve) will generate a smaller droplet size than the same pressure drop experienced over a longer time (e.g. pipeline). The lower the interfacial surface tension, the smaller the maximum droplet size that will be generated. The relationship described by the Hinze equation is illustrated graphically in Figure A.l for a range of typical values for an oil production facility. The mixing energies in Figure A.l range from 0.0010 mVs3 which is the mixing energy associated with the filling of settling tanks up to 100,000 m2/s3which is the mixing energy that may be imparted over a control valve. It can be seen that the stable droplet size over this range falls from 10,000 V r n for the low mixing energy to the order of 1 pm for high mixing energies. A stabilised emulsion would tend to generate even smaller maximum droplet sizes due to the lower surface tension and inhibition of coalescence.

A.1.3

Mixing energy in piping
The calculation of the mixing energy in piping and pipelines is relatively simple as both the location and duration of the pressure drop can be defined. The Reynolds number should first be calculated using equation A.3 or A.4. Re = p,xvxD

P
4XPc x q

Eq. A.3

Re =

rrxpxD

Eq. A.4

Where:

v p

D q

= = = =

flowing velocity (m/s) dynamic viscosity (kg/(m.s)) piping inside diameter (m) flow rate (m3/s)

From the Reynolds number, the flow regime may be identified and one of the following equations can be used to calculate the mixing intensity. Laminar flow Fie < 1500)
E=

512 x p x q2

n xp,xD

2

6

or

E=

32 x p x v2 pxD2

Eq. A.5

Turbulent flow /Re > 30001
&=

32xfxq3

n3 xD7

or

E=-

fXV3

2xD

Eq. A.6

Where:

q f

p D

= flow rate (m3/s) = friction factor read from a Moody diagram

= dynamic viscosity (kg/(m.s))
= piping inside diameter (m)

The friction factor f is the Moody-Weissbach friction factor and should not be confused with the Fanning friction factor. The friction factor may be read from a Moody diagram such as in the Shell Production
Poxe A-2
SIPM Deoiling Mor~iiol.EP 9.7-131.5, Hev I./. N(IV19Y3. Filv iwnir = YYAAI~INZ DOC

Appendix A - Emulsification and coalescence
Handbook, Volume 8, Pipelines, page 28, Figure 1.1-10. Alternatively, page 26 of the same reference presents an equation which can be solved to determine f. An example of the calculation of mixing intensity is included in Appendix B where it used to determine the isoenergetic sampling velocity.

A.2.

Optimum Mixina lntensitv For Coalescence
Using a dynamic coalescer, KSEPL have run laboratory trials to determine the optimum mixing energies that should be exerted upon a system to promote coalescence. The following results were obtained. Dehydration Deoiling Best coalescence in range of 2200 - 11,000 c m W with an optimum at 5500 cmVs3 Best coalescence in range of 11,000 - 110,000 cm2/s3

These optimum mixing energy figures are difficult to apply to conventional deoiling equipment where it can be difficult to identify the location and length of time that a fluid is exposed to mixing energy in the form of pressure drop. However, pipelines provide a readily identifiable source of mixing intensity. The mixing intensities given above can be used to evaluate the possibility of using a pipeline to promote coalescence. The full results of these coalescence tests can be found in reference 1.08.1.d. and this reference also includes discussions on the application of these mixing intensities to pipeline systems in Oman and Nigeria.

100000

v

Q
al

10000

a l

5

c

1000

_ .

-0

9

.!i
2

5

a
100

I
0.01 0.1 1

10

1 0.001 10 Mixing intensity (m*/s')
-D--

100

1000

10000

100000

...x..

. 1 mN/m

5mN/m

-30mN/m

Figure A.l Relationship between maximum droplet size and mixing energy for a selection of hydrocarbon surface tensions

SlPM nroiliiiji

Miiiiiiiil,

EP 93-13lS. Rrv I . 1. No11 199.1. File iiioiir = 99AAlllNZDOC

Puge A-3

Appendix A - Emulsification and coalescence

Appendix B - Sampling to determine droplet size

B.l.

Introduction
When sampling to measure a droplet size distribution, isokinetic sampling is required in the sample quill, however neutral conditions should exist in the majority of the sampling system. This method of sampling ensures that the droplet size distribution is not altered by the sampling procedure. In many cases, samples of dispersed hydrocarbons in water will be taken from relatively stable locations such as process piping where there is likely to be fairly neutral shear/coalescence behaviour. Thus the example calculation in this appendix actually demonstrates isoenergetic sampling, where the mixing intensity in the sampling system is kept equal to the mixing intensity of the process piping. In practice, the user should exercise their judgement in setting an acceptable mixing energy to maintain neutral behaviour in the sampling system. If the conditions at the point where the sample is taken are not neutral, the mixing energy in the sample system should be set to try and maintain neutral conditions. Some guidance on acceptable mixing energies can be found at the end of Appendix A. The following worked example is used to demonstrate the calculation of mixing intensities, the determination of the isoenergetic sampling rate and selection of the sampling quill size to achieve isokinetic sampling at the point where the sample enters the sampling system.

8.2.

Calculation of the mixina intensity in the process lint:
A sample is to be taken of an effluent water stream containing a relatively small quantity of dispersed hydrocarbons. The stream to be sampled has the following properties

p D p

q

= 790 m3/h = 0.2194 m3/s = 1025 kg/m3 = 0.3048 m internal diameter = 0.0006 Pa.s

From this information the mixing intensity being exerted on the fluid in the process line can be calculated using the equations presented in Appendix A. First the Reynolds number can be calculated from equation A.4.

-

R x 0.0006 x 0.3048

4 x 1025 x 0.2194

= 1,565,685
= 1,600,000

As Re > 3000, the flow is turbulent. From a Moody diagram, assuming that for clean steel the roughness is 0.02 mm, the friction factor f is 0.0124.
The mixing intensity E can now be determined from equation A.6.
E =

32xfxq

n3 xD’
32 x 0.0124 x 0.2194

E

=

n3 x 0.3048’

Appendix B - Sampling to determine droplet size
E

= 0.5530 m2/s3

E = 5530 cm2/s3

8.3.

Pressure drorJ in the samplina svstem
The sample is to be analysed to determine the size distribution of the dispersed phase and thus neutral sampling is to be used. The sample is to be taken in a pressurised sample bottle configuration as illustrated in Figure B.1. The sampling lines are nominal % inch outside diameter with an internal diameter of 15.8 mm. The overall length of piping in the system is 1.3m.

H Full bore isolationvalves

w Needle valve

-I) Quick release coupling

0

Total piping length
2 x full bore valves 1 x quick fit union, assume the same as a full bore valve 1 x straight through tee piece 2 x long radius bends Entrance loss into quill Exit into sample container

0
0

0

K K K K K K

-

= = = =

= =

1300 mm 1.3 m 3 x f (for each valve) 3xf 20 x f 12 x f (for each bend) 0.78 1.o

Losses after the last isolation valve will not affect the sample. The pressure loss within the sample container itself is assumed to be negligible.
2. Assume a samplina velocitv.

As the calculation is iterative a initial sampling velocity must be chosen. Try 1.O m/s as the initial guess. 3. Determine the samplina flow reaime in the samde line. The Reynolds number can be calculated from equation A.3. Re = pcxvxD
iJ

Re =

1025 x 1 .O x 0.0158 0.0006

R e = 26.992 Re= 27,000 As Re z 3000, the flow in the sampling lines is turbulent.

Puge 8 - 2

SlPM Droiliirg Mnnictrl, EP 93-1315. Rev 1.1, Niiv 1993, File ntrme = 99BBISO.DOC

Appendix B - Sampling to determine droplet size
4. Determine the friction factor, From a Moody diagram, the friction factor f for a Reynolds number of 27,000, an internal diameter of 15.8 mm and a roughness of 0.02mm is 0.027.

5. Determine the total flow resistances across the samplina svstem.
Knowing the friction factor, the total piping and fitting resistance KT can be determined. For piping, K = (f x L) / D, therefore; KT = KT=

(fxDL)
fX(

+ (2 ~
1.3

(x3 f)) + (1x ( 3 f)) ~+(20 x f) + (2 ~ ( 1 x 21)) +0.78 + 1.0

15.8 x

+ (2 x 3) + 3 + 20 + (2 x 12)

KT = 0.027~(135.2785)+1.78 KT = 5.4325
6. Determine the pressure drop across the samplina svstem.

The following expression for pressure drop is taken from the Crane reference, equation 3-14. AP = 5 ~ 1 x 0 K T~ xpx? AP = 5 ~ 1 0 ~ -5 ~. 4 3 2 5 ~ 1 0 2 5 ~ 1 . 0 ~ AP = 0.0278 bar AP= 2784Pa 7. Determine the time sDent in the samplina svstem. Assume that the pressure drop is spread relatively evenly through the sampling system. This assumption is reasonable as there are no large point sources of pressure drop in the sampling system and the pressure drop through the piping dominates. Thus, the duration of the pressure drop is the time taken to traverse the sample piping.

V

t t

= -

1.3 1.0

= 1.3seconds

8. Calculate the mixina intensity

E

=

2784 1025 x 1.3

E

= 2.0893 mVs3

E

=

20.893 cm2/s3

9. Assume a new samdina velocitv.

Now this mixing energy is significantly higher than the mixing energy of 5530 cm2/s3in the main process

Appendix B - Sampling to determine droplet size
line. We can get a closer result by assuming a lower velocity and recalculating. Assume new velocity of 0.65 m/s.

IO. Check the samplina flow reaime in the sample line.
Re = pcxvxD

m
1025 x 0.65 x 0.0158 0.0006

Re =

Re = 17,545 As Re > 3000, the flow in the sampling lines is still turbulent.

From a Moody diagram, the friction factor f for a Reynolds number of 17,545 an internal diameter of 15.8 mm and a roughness of 0.02mm is 0.0292. 12. Determine the total flow resistances across the samdina svstem. Recalculate the total piping and fitting resistance KT.

KT = 0.0292 x (135.2785) + 1.78
KT = 5.7301 13. Determine the pressure droD across the samplina svstem. AP = 5x1OW6xKT X AP =
~ X V

2

5 ~ 1 ~0 5.7 ~3 0 1 ~ 1 0 2 5 ~ 0 . 6 5 ~

AP = 0.0124 bar AP = 1241 Pa 14. Determine the time spent in the samdina svstem. The duration of the pressure drop is the time taken to traverse the sample piping.

t

= -

1.3 0.65

t

= 2.0seconds

15. Calculate the rnixina intansity

E
E

=

1241 1025 x 2.0

= 0.6054 m2/s3

E

= 6.054 cm2/s3

PURC8-4

SIPM Deoiliiig Mmiiwl, El' 93-1315, Rev 1.1. Nov 1993. File noinr = 99BBISO.DOC

Appendix B - Sampling to determine droplet size
16. Conclusions

The mixing intensity with a sampling velocity of 0.65 mls is very similar to the original mixing intensity in the pipeline. Thus 0.65 m/s is a suitable sampling velocity to achieve isoenergetic sampling.

B.4.

Sizina the sample quill for isokinetic conditions
The previous calculation has shown that the sampling velocity through the majority of the sampling system should be 0.65 m/s to avoid any changes to the droplet size distribution. However, as discussed in section 5.5, the fluid velocity in the sample quill itself should be isokinetic to ensure a representative sample enters the sampling system. The sampling velocity and size of the sample piping determine the overall volumetric sampling flow rate. We need to specify the size of the sampling quill such that isokinetic conditions are achieved at this flow rate.
1. Determine the overall volumetric samplina flow rate

The overall volumetric sampling flow rate C is calculated by multiplying the sampling velocity and the cross sectional area of the sampling piping. q , =
vx-

xxD2 4
-3

4 , = 0.65~

4

)2

q , = 1 . 2 7 4 4 ~ 1 0 -m3/s ~
2. Determine velocitv in the main Drocess line

The fluid velocity in the process line being sampled is calculated from the volumetric flow rate and the internal diameter. vp = 4xa nxD2 4 x 0.21 94

vp =

n x 0. 30482

vp = 3.0 m3/s

3. Calculate the size of sample quill to achieve isokinetic samDling
We now have the overall volumetric sampling flow rate and we know that to achieve isokinetic conditions the velocity in the sampling quill must be 3.0 m/s. From this information we can calculate the required internal diameter of the sample quill.

D , =

/

4 x 1.2744 x 10-4 ~ ~ 3 . 0

D , = 7.3544 x 10-3 m

D , = 7.35 mm

SIPM Deoiling M u ~ i r dEP , 93-1315. Hrv 1.1. N i w 1993. File 1 1 1 1 1 ~ 1 = ~ 99N11ISO.DOC

Puxe B-5

Appendix B - Sampling to determine droplet size
4. Conclusions

The sample quill should have an internal diameter in the order of 7.4 mm. With the velocity in the main sampling lines of 0.65 m/s, isokinetic conditions will be achieved in the sample quill and isoenergetic conditions will be achieved in the remainder of the sampling system. The sample quill should be kept as short as possible to avoid adding mixing energy to the sample.

8.5.

Contrast with iso-kinetic samDlinq
The mixing intensity calculated above can be contrasted with the pressure drop and mixing intensity that would be experienced if the entire sample system was operated at the isokinetic sampling velocity. 1. Determine the iso-kinetic samDlina velocitv. We know from the previous calculation that the isokinetic sampling velocity is 3.0 m/s.
3. Check the samplina flow reaime.

The Reynolds number in the sample line can be calculated from equation A.3.

Re =

1025 x 3.0 x 0.01 58 0.0006

R e = 80,975 As Re > 3000, the flow in the sampling lines is turbulent. 3. Determine the friction factor. From a Moody diagram, the friction factor f for a Reynolds number of 80,975 in an internal diameter of 15.8 mm and a roughness of 0.02 mm is 0.0235. 4. Determine the total flow resistances across the samplina system. Recalculate the total piping and fitting resistance KT.

K , = 0.0235 x (135.2785) + 1.78 K , = 4.9590
5. Determine the Dressure drop across the samDlina svstem.

AP = 5 ~ 1 0 ~ -4 ~. 9 5 9 0 ~ 1 0 2 5 ~ 3 . 0 ~
AP = 0.2287 bar

A P = 22874Pa
6. Determine the time spent in the samplina svstem.

The duration of the pressure drop is the time taken to traverse the sample piping
t
= -

L
V

E U ~ E-6 C

Appendix B - Sampling to determine droplet size
t = -

1.3
3.0

t

= 0.433seconds

7. Calculate the mixina intensity

E

=

22874 1025 x 0.433

E

= 51.5383 m2/s3

E = 515.383 cm2/s3
8. Conclusions

It can be seen that the mixing intensity from iso-kinetic sampling is in the order of two magnitudes higher than the isoenergetic sampling (which in this case i s assumed to be neutral). This highlights the importance o f not using iso-kinetic conditions throughout the whole sampling f the dispersed phase system and trying to maintain neutral sampling when the size distribution o is to be determined.

Appendix B - Sampling to determine droplet size

P U ~8-8 C

SlPM Deoilirtx

Mtriirctil. EP

YJ-lJ1.5. Rrv 1. I . Nos 1YY.1, Fllr

iltitiir

= 99BBISO.DOC

Appendix C - Published infrared analysis procedures

c.1

List of IR analvsis procedures

Test reference

Brief Designation API Method 733 58

Date

Title Determinationof volatile and non-volatileoil material. Infrared spectrometric method

Country 1U.S.A. Germany

Language IEnglish German

[l]
[2] [3] [4] [5] [6]
[7]
I

-

DEV H 17/181971

CONCAWE
~UNICHIM

I I
1971
I

Bestimmungvon Kohlenwasserstoffenmittels der lnfrarotintensitrits-Spektroskopie. (Determination of hydrocarbons by infrared intensity spectroscopy). Mineral oil in water by infrared spectrophotometry.

I

1972

I 1
I
U.S.A.
UK

Netherlands English

1975 IDeterminazionedegli oli mineral per spettrofotometria I.R. Italy

I

T91-502(1 977) 418.1
EPA 1978 lMCO1978

NBN

Dtltermination des hydrocarbures par spectrophotometrie Belgium infra-rouge. Bepaling van de koolwaterstoffendoor infrarood spectrofotometrie.

1978 1978 1979 1979

Petroleum hydrocarbons, total recoverable. (Spectrophotometric,infrared.) Method for the determination pf oil content. Effluents aqueux des raffineriesde petrol. Dosage des hydrocarburestotaux. Method of analysis for discharges from oil and gas production platforms. Methode d‘analyse pour les dtlversements des plateformes de production de gaz et d‘huile. Determinationof oil and grease in water. Infrared spectrophotometricmethod Bepalingvan de olie-index met behulp van infraroodspektrometrie.(determination of the oil-index by infrared spectrometry) Standard test method for oil and grease and petroleum hydrocarbonsin water. Partition-infraredmethod (tentative) Hydrocarbons. Water Bepaling van het gehalte aan minerale olie met behulp van infrarood-spectrofotometrie (Water Determinationof mineral oil content by infrared spectrophotometry)

I lDutch
French and English English French English and French France

IItalian

[8] [9]

T90-203/79
Paris Commission Commission de Pans

AFNOR

____
Sweden

[lo]
[ll]
[12] [13] [14]

Swedish Standard

SS028145 ( 1979)
RlZA

1979 1980 1980 1980 1989

Swedish

Netherlands Dutch

ASTM D 3921-80 APHA 1980 Parts 502B,502E NEN NEN 6675

U.S.A U.S.A

English English

-

Netherlands Dutch

1989

-

[I51

DIN DIN 38409 H18

1981

Bestimmungvon Kohlenwasserstoffen. (Determinationof hydrocarbons.)

Germany

German

Source: Determinationof hydrocarbons in aqueous effluents by infrared analysis, Concawe Report No. 1/84, March 1984. NEN method upgraded from

tiQ!.M
1.

NEN 6673 (1981) to NEN 6675 (1989).

2.

The informationcontained in this table has been reported as stated in the texts of the individual methods. No attempt has been made to amend it, even if it appears inconsistantin some cases. st: overall (total) standarddeviation so: single operator standard deviation

Appendix C - Published infrared analysis procedures
c.2
Kev characteristics of identified IR analvsis procedures

(Page 1 of 3) Test reference METHOD Matter revealed
[l] 121 API Method DEV H 17/18 733 58 1971 hydrocarbons, hydrocarbons hydrocarbon derivatives, all substances with CH, CH2, CH3 groups.

-

[3] CONCAWE

UNICHEM 1975

141

hydrocarbons, or mineral oils hydrocarbon derivativesof any kind

151 NBN T91-502 (1977) hydrocarbons

Minimum 1 determinability (ppm) 3 Sample volume (I) pH adjusted to Extractionsolvent Boiling point (“C) Volume (ml) Extractionperformed: In By means of For Chrornatogpaphic adsorbent Column diameter (cm) Height of filling (cm) Quantity (9) Matter removed Wavelength (pn) Groups detected Calibration 3.42 3.50 CH2 CH2 original container
5

0.1
1

0.1

0.5

0.2
1
5

3

variable
5

___cc14 77 25

5
cc14 77
50

CCI4 77

cc14 77
50

cc14

77
50

loo+ 100

original container

original container shaking machine 100 strokeshin, amplitude 3.8cm 15 min Florisil added

original container

original container

shaking machine 100 mechanical strirrer strokeshin, amplitude 3.8cm 15 min 30 sec Florisil added

magnetic stirrer (4 cm hand or shaking machine 100 strokes long) per minute 15 rnin 15 min Florisil added Florisil
1

5 to 6
1 5

5
non-hydrocarbonpolar components aceous polar organic compounds 3.38 3.42 3.30 3.38 3.42 CH3 CH2 known oil or typical absorptivities (one normal, one for gasoline) CH CH3 CH2

non-hydrocarbons 3.30 3.38 3.42 CH CH3 CH2

most of the nonhydrocarbons 3.38 3.42 CH3 CH2 know oil or typical absortivities (one normal, one for gasoline) in the case of gasolines less accurate values are to be expected repeatabilitybetter than 10%

Results reported Accuracy

Precision

known oil or reference typical specific oil (37.5% iso-octane, absorptivities for CH, 37.5% cetane, 25% C H , CH, bands benzene) to the nearest ppm < 10 to 0.1 ppm > 10 to 1 ppm about *lo% for not suitable for highly known oil, &O% for aromatic products reference oil, such as tar oil and benzene, xylene, aromatic extract cumene essentially undetected about *lo%

typical absorptivities for CH, CH2, C H : ,

less suitable for highly aromatic hydrocarbons

at 2pprn level st = 0.24 so = 0.06

reproducibility20%

Source: Determination of hydrocarbons in aqueous effluents by infrared analysis, Concawe Report No. 1/84, March 1984. NEN method upgraded from

I’ll@

c-2

SII’M D t w i / ; f Moriifol, !~ EP 93-1315, Rev I . I. Nov 1993. Filr

iiifiiie

= 99CCIRED.DOC

Appendix C - Published infrared analysis procedures
Table C.2 Published infrared procedures for determination of hydrocarbons in water (Page 2 of 3) [SI [7] [E] [9] IMCO 1978 AFNOR Paris Commission EPA 1978 418.1 T90-203179 1979 oils, including most petroleum oil, inclusive of most total hydrocarbons hydrocarbons light oil fractions light fractions inclusive of light fuels

Test reference METHOD Matter revealed

Minimum C1 determinability(ppm) 1 Sample volume (I) pH adjusted to Extraction solvent Boiling point ("C) Volume (ml) Extractionperformed: In By means of For Chromatographic adsorbent Column diameter (cm) Height of filling (cm) Quantity (9) Matter removed separatoty funnel hand 2 min silica gel added c2 Freon 113 48 30+30+30

0.1 1 <2 CCI4 or others 77 50+50

_-__
0.9 5 CClq

0.1 1 <2 CCI4 / Freon 113 77 I 4 8 50+50

Swedish Standard SS028145 (1979) most components in mineral oil, some organic solvents, petroleum based part ot greases, petroleum based waxes 0.1 1.2 c2 CCI4

[lo]

77
50

77
50

separatory funnel hand 2 min

original container

separatory funnel

separatory funnel shaking machine
60 min

magnetic stirrer ( cm hand long) 15 min 2 min florisil 1

*'2'3 1 10

3

5 other organic nonhydrocarbon matter separate detmn humic substance; high molecular aromatics; detergents, veg. fats, fatty oils, saponifiable grease, lactic fat, glycols, alcohols, ketones 3.38 3.42 CH3 CH2 known oil or reference oil (37.5% iso-octane, 37.5% cetane, 25% benzene) 10 to 0.1 ppm hydrocarbon mixture is used, i 30 40% in extreme cases. often better than i 2.5%
i 5 10% if

animal greases and vegetable oils

Wavelength (vm) Groups detected Calibration

3.41 CH2

3.41 CH2

3.42 CH2 known oil

3.41 CH2 known oil

Results reported Accuracy

known oil or reference known oil oil (37.5% iso-octane, 37.5% cetane, 25% chloro-benzene) c 10 to 0.1 ppm 10-1OOto1 ppm loss of about half of some loss of volatile any gasoline present componentswill can be expected occur

< 100 to 0.1 ppm

some loss of volatile components will occur

-

-

Precision

!l.Q.ks

Source: Determination of hydrocarbons in aqueous effluents by infrared analysis, Concawe Report No. 1/84, March 1984. NEN method upgraded from NEN 6673 (1981) to NEN 6675 (1989).

Appendix C - Published infrared analysis procedures
Table C.2 Published infrared procedures for determination of hydrocarbons in water (Page 3 of 3)

Test reference METHOD Matter revealed Minimum determinability (ppml Sample volume (I) pH adjusted to Extractionsolvent Boiling point (“C) Volume (ml) Extraction performed In By means of For Chromatographic adsorbent Column diameter jcm) Height of filling (cm) Quantity (9) Matter removed

[ll]

I

[12] D39251-80 petroleum

[13] APHA 1980 Parts 5028,502E hydrocarbons 0.2

NEN 6675 1989 mineral oil
0.05

r. i di .

I

IDIN 38409 H18 1981 hydrocarbons

r i 51
L._

I

10.1 10.5 1-2 Freon 113
48

0.8

2
Freon 113 148 30+30+30 Freon 113 Freon 113 77 20+20

i+15

P

30+30+30

25

separatory funnel hand or shaking machine 100 strokes/min. 2 min silica gel added

original container

Ioriginal container
or three dimensional

i min

2 min silica gel added

lrisil added

l2
I

3 oil and grease different from petroleum hydrocarbons

I

3 complex aromatic compounds, chlorine sulphur-nitrogenhydrocarbon derivatives; Freon insoluble material from heavier residue! 3.41

1

8

dar components

Wavelength (pm) Groups detected Calibration

42

I

3.41

octane, 50.0% cetane) Results reported Accuracy

1 0 0 to 1 ppm 100 to 10 ppm

,matics only rtially determined

to the nearest 0.1 ppm low-boiing organic materials are lost

Precision

d !Q .m ! .
1.

Source: Determination NEN 6673 (191

{drocarbons in aqueous effluents by infrared analysis, Concawe Report 0.1/84, March 1984. NEN method upgraded from 1 NEN 6675 (1989).

at a ppm level st = 0.160 a + 0.329 so = 0.141 a + 0.048

typical specific typical absorptivities absorptivities for CH, for CH, CH?, C H , C H , CH, bands bands or known oil or squalane or isooctane/cetane/benzen e 4 0 to 0.1 ppm >10tolppm less suitable for average recovery highly aromatic 97.2%; gasoline may products (tar oil and not be measured aromatic extract) (ratio of absorption at 3.30pm:3.42pm > 0.23) oil: (37.5% isooctane, 37.5% cetane, 25% benzene)

2.

The information contained in this table has been reported as stated in the texts of the individual methods. No attempt has been made to amend it, even if it appears inconsistant in some cases. st: overall (total) standard deviation so: single operator standard deviation

Pu,qe c-4

SlPM Dending Moniid. LP 93-1.jI5. Hrv 1.1. Nov 199.3. File nome = Y9CCIRED.DOC

Amendix D - Oil-in-watermonitor trials

D.l

Oil-In-Water Monitor Testina Phase I

-

D.l .l. General
The first series of trials of commercial oil-in-water monitors was conducted over the period of February 1989 to October 1989. The following report was issued and is available from SlPM EPD/421 on request. “Final report on the oil-in-water monitor testing conducted at Orkney Water Test Centre, February 1989 to October 1989”, Tullock, S.J., March 1990, EP-No.90-3673

D.1.2.

Monitors tested
The names, basis of operation and suppliers of the oil-in-water monitors tested in the Phase I trials are listed in Table D.l. It should be noted that due to installation problems no effective results were obtained for the Teledyne unit.

Oil-in-water monitor Bristol Babcock OCD-30 Facet Mark Vlll Bilge Alarm Horiba OCMA-25 Monitek Micro-Pure MPS-D Pure Alert Oili-S Type 300 Schlurnberger Oilcon EJB51 Teledyne 661R

Basis of operation Infraredlight scattering Infraredlight scattering Infrared absorption with solvent extraction Ultrasonic Direct infrared absorption Infrared light scattering Ultraviolet direct absorption

Supplier Bristol Babcock Ltd Facet Industrial UK Ltd Horiba InstrumentsLtd Monitek Technologies Inc OPTEC-InternationalLtd SchlurnbergerIndustries Ltd Teledyne Analytical Instruments Ltd

D.1.3.

Variables investigated
The variables listed in Table D.2 were investigated during the Stage I trials. As the Phase I oil-in-water monitor trials were integrated with other test work, the scope to freely adjust these variables or to repeat tests was limited.
Table D.2 Variables investigated for oil-in-water monitor trials Phase I

-

Variable Oil concentration Oil droplet size Free gas content Process chemical content Aromatic hydrocarbon content Oil density Solids content
6 to 30 prn.

Method I range 20-75 rngA while keeping droplet size relatively constant. Flotation or cyclone effluent, free gas not measured or controlled. Flotation aid, corrosion and scale inhibitor, demulsifier.

n g l toluene. Addition of 20 r
Normal oil/fuel oil.
14 and 60 mgA of sand, 300pm average particle size.

Appendix D - Oil-in-water monitor trials
D.1.4.
Summary of results
In general it was concluded that none of the monitors operated in a completely satisfactory manner, though some were clearly better performers than others. Due to the number of monitors and variables investigated it is not practical to fully summarise the results in this manual. Users requiring detailed information are referred to the original report. However the following significant points were noted from the trials. For monitors operating on light scattering principles, effective sample homogenisers are required to ensure the droplet size distribution reaching the instrument is consistent. Corrosion inhibitor was found to cause errors in the measured oil-in-water concentration. This effect was only observed when both corrosion inhibitor and hydrocarbons were present together in the effluent stream, but not when corrosion inhibitor was present by itself. This suggests an interaction between the hydrocarbons and the corrosion inhibitor.

All monitors were found to be insensitive to the level of dissolved aromatic hydrocarbons.

D.2 D.2.1.

Oil-In-Water Monitor Testina General

- Phase II

A second series of trials with oil-in-water monitors was conducted over the period of November 1990 to March 1991. The following report was issued and is available from SIPM EPD/421 on request.
“Oil in water trials conducted at the Orkney Water Test Centre, November 1990 to March 1991”, Tullock, S.J., Oct 1991, EP-No.91-2151

A summary of the OWTC Phase II trials can be found in the report;
“Commercial oil-in-water monitors - Evaluation and testing at the Orkney Water Test Centre”, Bannell, J.L.K., February 92, EP-No.92-0259

D.2.2.

Monitors tested
The names, basis of operation and suppliers of the oil-in-water monitors tested in the Phase I I trials are listed in Table D.3. The OCD-37, Monitek, Oili-S and Oilcon monitors were improved versions of the monitors tested in Phase I.

Oil-in-water monitor Fluoritest-S OCD-37 Monitek MPS-D Pure Alert Oilcon effluent monitor Oili-S Mark 1000 C Turner Model 10
I

Basis of operation Ultravioletfluorescence Infrared light scattering Ultrasonic Light scattering Direct infrared absorption Ultravioletfluorescence
I

Supplier Puskds Tivadar cooperative Rivertrace Engineering Ltd Monitek Technologies Inc VAF Instruments OPTEC-International Ltd Turner Designs

POKCD-2

SIPM Droiliiix Miriiiral. EP 93-1315, Rev 1.1. Niiv 1993, File nomc = 99DDMONS.DOC

Amendix D - Oil-in-water monitor trials
D.2.3.

Variables investigated
The variables listed in Table D.4 were investigated during the Stage II trials.
Table D.4 Variables investigated for oil-in-water monitor trials Phase I 1 Variable Oil concentration Oil droplet size Oil type Water temperature Free gas content Process chemical content Ambient temperature Long term operation Scaling Soluble hydrocarboncontent Oil density Solids content

-

I

Method I range 20-100 mg/l. 10,17.5,25 and 50 Mm. 36" Flotta crude, 21" fuel oil, 56" condensate.
7.5,25, 40 and 70°C.

Gas breakout in hydrocyclone effluent. Corrosion inhibitor, demulsifier. 15 and 25°C. Over a period of 21 days. CaCI2 and Na2C03 injection. Addition toluene and acetic acid. Normal oilMuel oil. Diatomaceous earth, 50pm average particle size.

D.2.4.

Summary of results
In general, in the Phase II trials it was again concluded that none of the monitors could be recommended as a reliable and accurate method to replace the manual sampling and analysis methods currently used for effluent water analysis. Due to the number of monitors and variables investigated it is not practical to summarise the results in this manual. Most of variables tested had some effect on the monitors, though the magnitude of the effect varied for each monitor. Users requiring detailed information are referred to the original report. However the following significant points were noted from the trials. The performance of the units was significantly better than the Phase I trials. Most of the instruments measured oil concentrations to *lo%.

Most of the monitors tended to over estimate the hydrocarbon content when using 56 "API condensate, even after recalibration.
None of the monitors tested detected the presence of dissolved hydrocarbons (toluene and acetic acid). (The Fluoritest-S and Oili-S monitors were not operational for this test.) The Performance of the monitors deteriorated in the presence of free gas and solids. However not all monitors were operational for this test.

SIPM Droilinl: Manrtul. EP 93-1315. Rev 1.1. NOV 1993. Filr

~I<III= I~

99flflMONS.flOC

Page 0 - 3

Appendix D - Oil-in-water monitor trials

D.3

Oil-In-Water Monitor Testina Phase 111
A third phase of oil-in-water monitor trials are to be conducted at the OWTC in the second half of 1993.
In the lead up to this trial a desk study was conducted by the OWTC to identify the range of oil-in-water monitors commercially available. A total of 34 instruments were identified from 19 different companies. The results of this study are summarised in the report; "Further developments in oil-in-water monitor technology Phase II. Monitor selection, Desk study report", Tullock, S.J., June 1993 The report includes a summary sheet for each instrument detailing the mode of operation, operating ranges etc. The report may be requested from SlPM EPD/42 if required. From the results of the desk study, the six instruments listed in Table D5 were selected for detailed evaluation in the Phase Ill oil-in-water monitor trials.
Table D.5 Oil-in-water monitors tested OWTC Phase 111 Oil-in-water monitor Vortoil D-100 Rivertrace Engineering OCD-100

-

I

-

Basis of operation Laser particle sizing

IR light scattering

I

Auuendix E - Particle size analvser trials

E.l.

OWTC particle size analvser trials

E.l .l. General
A selection of particle size analysers were tested at the OWTC over the period of November 1990 to February 1991. The following report was issued and is available from SlPM EPD/42 on request.
“Particle size analyser trials conducted at the Orkney Water Test Centre November 1990 - February 1991”, Tullock, S.J., Oct 1992, EP-No.92-1952

E.1.2.

Analysers tested
The names, basis of operation and required sample conditions of the particle size monitors tested is listed in Table E.l.
Table E.l Particle size analysers tested at OWTC Particle size analyser Coulter LS130 Coulter Multisizer Galai CIS-1002 Lasentec Partec 250 Malvem Mastersizer Basis of operation Laser diffraction Aperture counting Laser time of transition Fonvard scattering Sample Condition Batch, sample depressurised. Batch, sample depressurised, sample dilution may be required. Continuous, at process conditions up to 12 barg. Continuous, analysis probe can be inserted directly into the process piping (up to 10 barg). Batch or continuous, sample depressurised.

Laser time of transition Backward scattering Laser diffraction

E.1.3.

Variables investigated
The variables listed in Table E.2 were investigated in the OWTC particle size analyser trials.

Variable Hydrocarbondroplet size Hydrocarbondroplet concentration Hydrocarbon type Free gas content Solids content

range Method I

5 to 50 pm
20 to 100 mgA

21 API heavy oil, 56” API condensate
Nitrogen injection Diatomaceous earth (approx. 50pm median diameter)

E.1.4.

Summary of results
All of the analysers except one were found to perform well. Users requiring detailed information are referred to the original report.
Of the analysers tested, the Galai appeared to be particularly promising as it supported the following functions:

SlPM Deoilirig Moriiinl. EP 93-121.(, R n ’ 1.1. NIIV 199.1. File iiww = 99fiLSIZLDOC

Puxe E-1

Appendix E - Particle size analyser trials
Sampling and analysis at process operating conditions. This avoids sample depressurisation, potential gas breakout and changes in the droplet size distribution. At the time of writing the allowable sampling pressure had been increased to 80 bar and a version certified for 120 bar is expected in the near future. The instrument supports imaging facilities and shape analysis of the droplets and particles present in the sample.
9

The instrument is readily portable and will give instant results on site.

In view of the promising results from the OWTC trials and the potential advantages of the instrument, KSLA have conducted an investigation to compare the performance of the Galai with the KSLA method of microphotographyand image analysis. The results of this comparison are summarised in the following section.

E.2. E.2.1.

Galai CIS-1000trials at KSLA Results of trial
Following promising results in the OWTC trials, the Galai CIS-1000 size analyser was further tested at KSLA to compare its performance against the KSLA micro-photographic technique (March - April 93, Ref. 1.4.2.b). The following results were found; In general the size distributions measured by the Galai compared well with the KSLA method. However under some operating conditions inaccurate results were recorded from the Galai. At a certain sampling velocity, a step change in the droplet size distribution as measured by the Galai was observed. This effect may be due to distortion of the shape of the dispersed droplets at higher sampling velocities.

If there are too few dispersed droplets the Galai may not be able to give a result. This may be a problem at low hydrocarbon concentrations or with a relatively small number of large droplets.
If there are too many droplets, interference with the laser may result in incorrect results. There is some doubt over the ability of the instrument to clearly differentiate between liquid droplets and solid particles. The original orientation of the sampling cell allowed bubbles to accumulate and coalesce until a single large bubble detached and passed through the measuring system. This was corrected by altering the orientation of the sampling cell.

E.2.2.

Conclusions
Although under most conditions the Galai size analyser was found to give a droplet size distribution comparable to the KSLA size analysis technique, there appear to be certain operating conditions where the results from the Galai are not reliable. At this stage, further work is required to clearly define the operating envelope in which the user would be confident of obtaining representative results from the Galai, particularly with respect to the sampling velocity and droplet population density. Until the operating envelope is more clearly defined the Galai cannot be recommended as a suitable method for measurement of droplet size distributions in the field. Vortoil are developing a version of the Galai (the D-100) which with new software will be able to measure both droplet size distribution and to infer the concentration of dispersed hydrocarbons. The unit is Ex qualified for use in hydrocarbon areas and may have significant promise as a trouble-shooting diagnostic tool for water treatment equipment. The potential advantages of the Galai or Vortoil instruments for on-site measurement of droplet size distributions at operating conditions means that further test work is recommended. SlPM EPD/42 should be contacted to determine the current status of development .

Puxe E-2

SlPM Duoiliiil: Mwiud, EP 93-1315, Rev 1.1. Nriv 1993, File noine = 99EESIZE.DOC

Appendix I; - Stokes Law

F.l.

Derivation
Provided a density difference exists between the hydrocarbon phase and the water phase, a dispersed hydrocarbon droplet will experience a buoyant force as expressed by equation F.l.

Eq. F.l buoyant force (N) gravitational acceleration, (m/s*) dispersed droplet size (m) density of the continuous water phase (kg/m3) = density of the dispersed hydrocarbon phase (kg/m3)

where:

F , g d pw ph

= = = =

In most cases the hydrocarbon density will be lower than that of the water phase and the dispersed droplet will experience a positive buoyant force causing the droplet to rise upwards.

As the droplet rises through the continuous phase, the buoyant force will be opposed by a drag force on the droplet. The drag force is expressed by equation F.2
Eq. F.2 drag force (N) drag coefficient dispersed droplet size (m) density of the continuous water phase (kg/m3) droplet velocity relative to the continuous phase (m/s)

where:

= = = pw = v =

2

Fd

When the buoyant forces and drag forces are in balance the droplet will rise with a constant terminal velocity vT. For a dilute dispersion of small hydrocarbon droplets in a water phase the Reynolds number is generally less than 10 and the following approximation for the drag coefficient may be used. 24 =Re

cd

Eq. F.3

where:

Re =
p

pwxvxd

P

= dynamic viscosity (Pa.s or kg/(m.s) or cP/lOOO)

Equating the equations for the buoyant and drag forces (F.l and F.2) and substituting the approximation for the drag coefficient (F.3) and Reynolds number results in the derivation of Stokes Law, as expressed by equation F.4.

Eq. F.4 Where: vT

= terminal droplet rising velocity relative to the continuous phase (m/s)

SIPM DeoiliiiK Mmrtal. EP 93-1315, Rev 1.1. Nov 1993. File iiiisir = 99FFSTOX.DOC

Puxe F-I

Appendix F - Stokes Law
F.2. F.2.1 Variables In Stokes Law Droplet size
As the terminal rising velocity of a hydrocarbon droplet is proportional to the square of the droplet diameter, it is highly desirable to maximise the droplet diameter. This can be achieved by avoiding shear forces and promoting droplet coalescence wherever possible.

F.2.2

Gravitational acceleration
The acceleration force due to gravity is constant at 9.81 m/s*. However hydrocyclones and centrifuges operate by imposing a centrifugal acceleration on the system. This centrifugal acceleration can be several orders of magnitude higher than gravitational acceleration and will increase the terminal rising velocity of a droplet proportionally.

F.2.3

Viscosity
The terminal rising velocity is inversely proportional to the continuous phase viscosity. Lowering the viscosity of the continuous phase (e.g. by raising the temperature) will increase the rising velocity.

F.2.4

Density difference
There must be a density difference between the two phases for the hydrocarbon droplet to experience a buoyant force. The larger the density difference, the larger the terminal velocity. In most cases the hydrocarbon phase will be less dense than the water phase, leading to a rising hydrocarbon droplet. The density of each phase will change with temperature. The effect of temperature on the terminal rising velocity of a hydrocarbon droplets is discussed further in Section F.3.

F.3.

The Effect Of TemDerature On Stokes Law
Changes in the temperature of a water stream containing dispersed hydrocarbon droplets .will influence the viscosity and density of both phases. Changes in the hydrocarbon phase viscosity will not have a significant effect on the droplet velocity, however, changes in the water viscosity will have an inversely proportional effect on the droplet velocity as discussed in F.2.3. Raising the temperature will reduce the water viscosity, reducing the drag forces and increasing the rising velocity of the hydrocarbon droplet (or falling velocity if the droplet has negative buoyancy). Changes in temperature will also affect the density of each of the phases. However, the rate of density change with temperature for each phase may be different, thus the density difference between the phases may be a function of temperature. Figures F.l to F.3 illustrate potential changes in viscosity and density for three emulsions. Figures F.4 to F.6 illustrate the effect of these changes on the droplet terminal velocity.

J , as the temperature All three emulsions exhibit a decrease in the continuous water phase viscosity I rises. The defining characteristic for each type of emulsion is thus the variation of the density difference between the phases with temperature.
Type I emulsions have a continual widening of the density difference with temperature. Thus as shown in Figure F.4 the terminal velocity increases with increasing temperature. Type II emulsions have a narrowing of the density difference between the phases as the temperature rises. Thus as illustrated in Figure F.5 the terminal velocity will reach a maximum value at an optimum combination of viscosity and density difference and then will start to fall. Further increases in temperature beyond the maximum terminal velocity will be detrimental to the separation. In Type I l l emulsions, different rates of density variation with temperature result in a crossing of the density-temperature curves for the two phases. At the temperature where the curves cross, there will be no density difference and the droplet will be neutrally buoyant. As the temperature increases further the system will invert with the hydrocarbon droplets becoming denser than the water phase and falling rather than rising through the continuous water phase. This behaviour has been observed numerous times in heavy oil fields. This behaviour highlights the influence of temperature on Stokes law. Examination of Stokes law

POKCF-2

SIPM Deoiliiih. Maiirtrtl. EP 9.1-1315, KKV 1.1, N:IV 1993, File nrimr = 99FFSTOK.DOC

Appendix I; - Stokes h w
illustrates that for a given droplet size and gravitation force the terminal velocity is only proportional to the density difference and the continuous phase viscosity Le. vt a
(Pw -PtJ

CI

This term, formed by the density differential divided by the viscosity is known as Stokes parameter.
e

1L

x c .-

a 5

c

J
0 50

E
Temperature "C
100 150
H7$a7xmY

W 0 .

i71/(

+

50

Temperature "C

100

1

150

Figure F.l Type Iemulsion: Viscosity and density vs temperature

Figure F.4 Type Iemulsion: Terminal velocity vs temperature

Pw

'8
c
_ I

i?
W

-

:

I

0

50

Temperature "C

100

150

g +
I

I

50

Temperature "C

F

100

150

l

Figure F.2 Type II emulsion: Viscosity and density vs temperature

Figure F.5 Type II emulsion: Terminal velocity vs temperature

I o

50

Temperature "C

100

I5O

I

I
Figure F.6 Type 111 emulsion: Terminal velocity vs temperature

Figure F.3 Type 111 emulsion: Viscosity and density vs temperature

Appendix I; - Stokes Law

HIS P INTENTIONALLY LE

NK

Puxe F-4

SlPM Deniliiil: Monucil, EP 93-1315, Rev 1.1. Nov 1993. File ncrme = 99FFSTOK.DOC

Appendix G - Coalescer equipment and trials

G.1.

Introduction
The equipment presented in these discussions represents a range of coalescers known to SlPM through trials, installations or vendor contact. Presentation in this manual does not suggest a particular preference for any particular equipment or supplier and specific equipment brands should be considered as illustrative of the various generic classes of coalescer.

A number of these coalescer designs have been tested at the OWTC. The results of the tests are contained in the report;
“Testing of coalescing devices to enhance the performance of hydrocyclones at Orkney Water Test Centre”, Webster, J.D., March 1992, EP-No.92-0942. Some of the results are briefly summarised in the following discussions and in Figures G.7 to G.9.

G.2. G.2.1

Knitmesh Dusec Description
The Knitmesh Dusec is a cartridge type coalescer consisting of a selection of fibres arranged in layers around a central perforated cylinder. The Dusec cartridge design should not be confused with the simpler Knitmesh DC coalescing mesh (though the outer layer of the Dusec cartridge does utilise the DC mesh).
As illustrated in Figure G.l, the feed enters the centre of the cartridge and flows radially through the coalescer. A mixture of hydrophilic and oleophilic fibres is used with the junctions between the different fibres acting as sites for coalescence. Dispersed droplets are captured on the oleophilic fibres and grow as additional droplets are intercepted.

Eventually the droplets grow to such a size that viscous drag forces acting on the droplet (as a result of the continuous fluid flow through the coalescer) will dislodge the coalesced droplet from the coalescing media.

G.2.2

Packaging
A number of coalescer elements are typically installed on a mounting sheet as illustrated in Figure G.l

Water outlet

U 4 II

I

Oil outlet

!

I/ I

Figure G.l Typical Knitmesh Dusec coalescing cartridge installation

Appendix G - Coalescer equipment and trials
The system may be packaged as a combined coalescer separator as illustrated in Figure G.1, or as a smaller vessel without separation capability upstream of conventional deoiling equipment such as a plate pack interceptor or a hydrocyclone package.

G.2.3

Performance
The Knitmesh Dusec cartridge has been tested at the OWTC and found to effectively coalesce condensate and medium density crude oil. Results were not as favourable for heavy crude oil (see Figures G.7 to G.9). The Dusec cartridge has also been successfully tested for the removal of water from condensate (Ref.2.14.2.c). Similar cartridge type coalescer elements are available from a number of suppliers such as Peco, Alan Cobham, Plenty and Warner Lewis. These cartridges are manufactured from a range of materials such as fibreglass, polypropylene and paper. A number of these cartridges have undergone laboratory trials to measure their performance in the removal of dispersed water from condensate (Ref.2.14.2.c and 2.14.2 .d) .

The Knitmesh DC is a coalescing mesh composed of dissimilar materials, typically a metal and a plastic material. The junctions formed between these materials are believed to improve the coalescing performance of the mesh. The DC mesh is designed for use as a primary coalescing material for relatively large dispersed droplets and would be typically installed vertically across a horizontal separator. The Knitmesh DC coalescing mesh has been used successfully at the Shell Stanlow and Pernis refineries. The Knitmesh DC mesh is also used as the outer layer on the previously discussed Knitmesh Dusec coalescing cartridge.

G.4. G.4.1

tivdrocvclone coalescer
Description
In addition to the normal use of hydrocyclones for hydrocarbon/water separation, hydrocyclones may also be used as coalescers. In coalescing mode the centrifugal forces generated in the hydrocyclone concentrate hydrocarbons at the core of the cyclone, where if conditions are favourable they have a higher probability of coalescence (due to the higher concentration of droplets). In coalescing mode the hydrocarbon reject port is blanked off and the coalesced hydrocarbons leave with the water stream from the underflow of the cyclone. In coalescing mode the cyclone is operated at throughput lower than the normal separation capacity. In the case of the Vortoil F liner design, Vortoil recommend that in coalescing mode the cyclone is operated at 6.6 mVh, compared to the nominal 8.1 m3/h capacity for normal separation duties. A recycle stream can be used to improve the coalescing performance of the hydrocyclone.

G.4.2

Packaging
Packaging is similar to the normal hydrocyclone systems discussed in section 8.9. The normal hydrocarbon reject port is blocked off and a recycle stream may be used to aid coalescence. The coalesced stream would typically be used as feed to a downstream set of separation hydrocyclones.

G.4.3

Performance
A Vortoil hydrocyclone operating in coalescing mode has been tested at the OWTC with generally favourable results with good coalescence of droplets smaller than 20 pm. For condensate and light oils the coalescing efficiency improved significantly with a 50% recycle. However for heavy oils the performance deteriorated with a recycle (see Figures G.7 to G.9).

PURCC-2

SIPM Dcoiliiix Mctr~irrrl.EP 93-1315, Rev 1.1. Nov 1993. File noinr = 99GGCOAL.DOC

Amendix G - Coalescer eauiument and trials
G.5. G.5.1 MPE SP Pack Description
The SP Pack is a free flow coalescer in which the oily water travels through a serpentine path. The turbulence and residence time in the pack is designed to promote coalescence. The unit is designed to avoid droplet shearing and does not have small passages that could be blocked by solids in the feed stream.

G.5.2

Packaging
The SP pack is packaged box enclosing the serpentine flow path and is designed to be installed internally in tanks or vessels. The internals of the SP Pack are generally constructed from PVC and fibreglass.

G.5.3

Performance
Testing at the OWTC indicated that for low oil concentrations (<400 mg/l) the SP Pack had a coalescing efficiency only in the order of 10% for droplets smaller than 40 Vm (see Figures G.7 to G.9). Performance was better for higher hydrocarbon concentrations in the order of 800 mg/l. This performance is unlikely to make a significant improvement to most downstream deoiling separation equipment, with the exception of gravity based separators such as skimming tanks. The SP Pack design has been used successfully in the USA, installed on the inlet feed to a skimming tank for the coalescing of relatively large hydrocarbon droplets (Ref.2.14.2.b).

G.6. G.6.1

Monosep SDiralsep Coalescer Description
The Spiralsep coalescer takes the form of a simple spiral element installed in-line in piping. The fluid flow is forced into a spiral path around the core and the centrifugal forces generated should assist hydrocarbons to migrate to the core of the spiral where they may coalesce.

G.6.2

Packaging
The Spiralsep unit is an in-line coalescer and is installed as normal piping. A minimum liquid velocity in the order of 4.3 m/s is required through the unit to promote coalescence.

G.6.3

Performance
Testing at the OWTC indicated that for low oil concentrations (<400 mg/l) the Spiralsep had a relatively poor coalescing efficiency for droplets smaller than 40 Vm (see Figures G.7 to G.9). Performance was better for hydrocarbon concentrations in the order of 800 mg/l.

G.7. G.7.1

Sulzer MellaDak Description
Mellapak is a structured packing constructed of either stainless steel or polypropylene. The vendor considers polypropylene more suitable for oily water applications due to its oleophilic nature.

G.7.2

Packaging
The Mellapak may be manufactured to any reasonable diameter or shape.

G.7.3

Performance
Testing at the OWTC indicated that the Mellapak structured packing only exhibited significant coalescing properties with hydrocarbon concentrations in the order of 800 mg/l (see Figures G.7 to G.9).

Appendix G - Coalescer equipment and trials
G.8.
Uoflow Filter/Coalescers
The principle of the upflow filter coalescer is illustrated by the Natco VFX design in Figure G.2 The media bed acts as a filter for suspended solids in the feed. However the filter is operated to force hydrocarbons upwards completely through the filter bed. This promotes the hydrocarbons to coalesce and they leave the top of the filter bed as relatively large droplets which are collected and removed from the top of the vessel. This basic design is used in both the Natco VFX and the Degremont Colexer filter/coalescers. The Natco design includes a layer of coarse oleophilic material on the top of the filter bed to assist the coalescence of the hydrocarbons. The Degremont design uses injection of a polyelectrolyte to create an oleophilic surface on the filter media particles. In both designs clean water is withdrawn from the side of the vessel above the filter bed (using baffles to ensure rising hydrocarbon droplets are excluded) and the filter is cleaned by backwashing to expand the filter bed.
Oil out
Filter

Backwash

Coarse Lipophilic

~

Coarse Garnet

Raw water in -..-

Figure G.2 The advantage of the filterlcoalescer designs would Natco VFX filterlcoalescer appear to be the longer filtration cycle times compared to filtration only processes. This is because the length of the filtration.cycle will be governed by the solids loading rather than the hydrocarbon loading. However there are several potential disadvantages with the filter/coalescer design. The best coalescing performance would be expected with relatively high oil contents (>lo0 mg/l). However, this conflicts with deep bed media filtration experience which suggests fouling of the media bed can be a significant problem with high hydrocarbon concentrations or heavy oils. It is not known whether the media coalescer would be subject to same problems with fouling and “mudballing” of the media. In addition, due to the upflow configuration, the flux rate through the bed will be limited by the need to avoid bed fluidisation. The normal filtration/coalescing fluxes are in the order of 18 to 20 (m3/h)/m2. There are no known installations of the Natco VFX or the Degremont Colexer filter/coalescer within the Shell group.

G.9.

Expandable fibrous bed coalescer
In recognition of the problem of blockage of coalescing devices with solids, KSEPL/TRC developed the expandable fibrous bed coalescer illustrated in Figure G.3.The unit consists of a bed of polypropylene fibres which can be expanded during the periodic cleaning cycle to remove entrained solids, then recompressed for coalescing duties. The fibres themselves are permanently surface treated to enhance coalescence. The expandable fibrous bed coalescer has so far not been developed for commercial exploitation.
H7502w3BP

out

Backwash

Operating mode

Figure G.3 Expandable fibrous bed coalescer

Backwash in Backwash mode

Puge G-4

SlPM DrorlrriC: Mcriiutrl. EP 93-1315. Rev I I. Nov 1993, File ncrmr = 99GGCOAL.DOC

Appendix G - Coalescer equipment and trials
G.10.
Skimovex lnverto Filter/Coalescer
The Skimovex lnverto filter coalescer, illustrated in Figure G.4, is a filterkoalescer based on downflow deep bed filtration. The filter is designed to trap solids in the filter bed while hydrocarbons are coalesced by being forced downwards through the filter bed. The filter is packaged as a dual unit with the feed to the on-line unit backwashing the off line unit. Skimovex claim that the solids collected in the filter bed tend to partition to the oil phase during the backwash and will be collected in the upper head of the off line vessel with the coalesced oil released from the filter bed.

s

Upflow

Oil

Downflow

b

As with the upflow filterkoalescers, the advantage of the filter/coalescer designs would appear to be the longer filtration cycle times compared to filtration only processes as the length of the filtration cycle will be governed by the solids loading rather than the hydrocarbon loading. As the filterkoalescer is designed to carry hydrocarbons through the filter bed and is operating in a downflow configuration, the flux rate through the filter is claimed to be high, in the order of 2 to 3 times higher than a conventional downflow filter.

downstream separation

To

Figure G.4 Skimovex lnverto filter/coalescer

However, as with the upflow filterkoalescers the best coalescing performance can would be expected with relatively high oil contents (3.100 mg/l). However, this conflicts with deep bed media filtration experience which suggests fouling of the media bed can be a significant problem with high hydrocarbon concentrations or heavy oils. It is not known whether the media coalescer would be subject to same problems with fouling and “mudballing” of the media. There are no known installations of the Skimovex filterkoalescer within the Shell group.

G.11.

Elf Anvar Filter/Coalescer
The Elf Anvar system uses an oleophilic resin as the filterkoalescing media. The design is available in both upflow and downflow models. The upflow model, illustrated in Figure G.5, acts as a coalescer. The hydrocarbons in the water form a film around the oleophilic resin. The film detaches from the top of the resin bed as large coalesced droplets which can be readily separated.
removal

O l i

Packi
Deoiled water

Treated

water

Oily m

Figure G.5 Elf Anvar upflow coalescer

“,Y)26110P

YTLOmIP

Figure G.6 Elf Anvar downflow filter/coalescer with integral gravity separation compartment

The resin bed thickness is in the order of 300 mm with an allowable fluid flux of 12.5 to 20.0 (m3/h)/m2. The inlet stream would typically contain 10-100 mg/l of dispersed hydrocarbons with a claimed outlet hydrocarbon concentration below 1 mg/l. Most applications to date have been in the deoiling of relatively
~~~

SlPM D r o i l t n ~ Mmiiitl. EP 93-1315, Rev 1.1, NOV199.7. Tilt, ii(tiiie = 99C;GCOAL DOC

Pqe

G-5

Appendix G - Coalescer equipment and trials
clean boiler feed water, achieving claimed outlet hydrocarbon concentrations lower than 1 mg/l hydrocarbons. The upflow configuration should not be used in the presence of suspended solids. The downflow model is more suited to the presence of suspended solids, though the maximum solids concentration should be lower than 30 mg/l. Solids are trapped in the filter bed while hydrocarbons are coalesced by their passage through the bed. The relatively large coalesced hydrocarbon droplets are then separated by subsequent gravity separation. Figure G.6 illustrates an Elf Anvar downflow filter design incorporating an integral separation section above the filter. The filter is cleaned by backwashing and gas scouring. Claimed performance has been a reduction of 7500 mg/l and 500 mg/l hydrocarbons to below 50 mg/l and 15 mg/l respectively. The maximum flux rate is 10 (m3/h)/m2. For both upflow and downflow designs, the performance of the resin can be expected to gradually deteriorate due to fouling. Resin life is expected to be in the order of 2 to 3 years. There are no known operating installations of the Elf Anvar filter/coalescer within the Shell group.

G.12.

Plate interceptors
Plate interceptors are widely used for the coalescence and separation of dispersed hydrocarbons from water. The close spacing of the plates (20-40mm) ensures that the flow regime between the plates is laminar, allowing small hydrocarbon droplets which would normally be dominated by turbulence to rise relatively unhindered. The proximity of the plates ensures that a hydrocarbon droplet only has to rise a short distance before it intercepts the underside of a plate. The concentration of hydrocarbon droplets on the underside of the plate promotes coalescence of the hydrocarbon droplets. Plate pack interceptors are generally packaged to achieve both coalescence and separation. They are discussed in detail in Section 8.8.

G.13.

Natco Performax
Natco Performax is a coalescing matrix designed to be fitted across horizontal separation vessels. The matrix acts in a similar manner to a plate pack interceptor, reducing both turbulence and the rising distance to improve phase separation. The Performax matrix may either be installed as original equipment to minimise the size of the separation vessel, or may be fitted to most separators to improve throughput or separation performance. The matrix has also been used to minimise the effect of wave motion in separators located on floating production vessels. The Performax matrix has been successfully fitted to Shell Expro locations (Lowestoft and Leman).

P U ~ G-6 C

SlPM Deoilircl: Mnriiccrl. EP 93-1315. Rev 1.1, Nov 1993. File rcctnir = 99Cc'COAL.DOC

Appendix G - Coalescer equipment and trials

Droplets c 10 pm

Droplets c 20 pm

I I Droplets < 40 pm

1

Figure G.7 Comparative performance of coalescers 200 mgh of 56" API condensate (Dispersed in sea water at 55"C, 20 pm median droplet size)

60

40

v

8

h

20

'

Q m
C .-

m

-40
-60

. -

. .

-

. .

-80

-1 00

1

Droplets < 10 pm

Droplets < 20 pm

I I Droplets < 4 0 4

Figure G.8 Comparative performance of coalescers 200 mg/l of 37" API crude oil (Dispersed in sea water at 55"C, 20 pin median droplet size)

Appendix G - Coalescer equipment and trials

-1 00

L

Droplets < 10 prn

Droplets < 20 pm

Droplets < 40 prn

Figure G.9 Comparative performance of coalescers 400 mgA of 21" API heavy oil (Dispersed in sea water at 5 5 T , 35 pm median droplet size)

P U ~ G-8 C

SIPM Deoiliitx Miiitwl, EP 93-1.715. Re\, 1. I , Nov 1993. File mmr = 99GGCOAL.DOC

Appendix II - Plate pack sizing

H.l.

Introduction
The following equations can be used for the preliminary sizing or performance evaluation of plate pack interceptors. For detailed engineering sizing the user is referred to appropriate equipment vendors or the Shell documents referenced at the end of this Appendix.

H.2.

Revnolds number
The Reynolds number through a plate pack should be 800 or lower for flat plates or for corrugated plates when the flow is in the direction of the corrugations. The Reynolds number should be less than 400 if the flow direction is across corrugated plates.
It should be noted that the Reynolds number does not constrain the capacity of the plate pack, only the frontal area of the plate pack. For example, a pack with a Reynolds number restricted to 400 will require a wide frontal area, but due to the low velocity through the pack, can achieve the required droplet separation in a short pack length.

A plate pack with an allowable Reynolds number of 800 can have a smaller frontal area, but due to the higher velocity through the pack will require a longer pack length for separation. The actual flow capacity, separation ability and plate pack volume of each pack will be the same. Just the aspect ratio between the pack frontal area and pack length will be different. This is demonstrated in section H.5. The Reynolds number for flow between two plates can be calculated from the following equation. Re = Where:
pw = water density (kg/m3) p v
= dynamic viscosity (poise or kg/(m.s)) = water velocity (m/s)

pw x v x 4 x R H

P

Eq. H.l

R ,

= hydraulic radius (m)

The hydraulic radius RH is strictly defined as: RH = area of stream cross section wetted perimeter
Eq. H.2

For a rectangular flow channel, the hydraulic radius is: RH = Where: wxx 2 x (w + x ) Eq. H.3

x W

= Spacing between plates (m) = Width of plates (m)

However, for most cases, W >> x, thus equation H.3 can be simplified to: RH = 2 Substituting H . 4 into H.l Re =
pwx v x 2 x x
CI
X

Eq. H.4

Eq. H.5

Now, the velocity v through the plates is equal to the overall volumetric throughput divided by the plate pack area A. Therefore,

Appendix H - Plate pack sizing
Re = Where: q A
pw x q x 2 x x

PXA

Eq. H.6

= volumetric flow through the whole plate pack (m3/s) = plate pack cross sectional area (m*), = Width of pack (W) x Height of pack (H)

H.3.

Plate Dack dimensions for droDlet interception
The dimensions of the plate pack must be such that a hydrocarbon droplet will have sufficient time to rise and intercept a plate before being carried through the plate pack. To achieve this the dimensions of the plate pack should satisfy the following expression. LxA= Where: qxx
C O S ( ~ ) X V TXF

Eq. H.7

8

L
VT

= inclination of plate pack (horizontal = O", vertical = 90') = plate length in the direction of flow (m)

F

= terminal rising velocity of hydrocarbon droplet (m/s) (Eq. F.4, Appendix F) = 0.9 (Factor to allow for turbulence in initial sections of plate pack)

Equations H.6 and H.7 may be used either to calculate the required size of plate pack to achieve a specified separation duty or to determine the potential separation performance of an existing or standard sized plate pack.

H.4.

Sizina a plate pack
The following example illustrates the sizing of a plate pack to achieve a desired separation at a given capacity.

Example
Determine the dimensions of a plate pack required to separate hydrocarbon droplets of a given size. For example, determine the size of plate pack required to separate 60 pm hydrocarbon droplets from a waste water stream of 80 mVh. Assume a rectangular plate pack, a water density of 1000 kg/m3, hydrocarbon density of 900 kg/m3, water viscosity of 0.8 cP.
1.

Assuming the water stream is relatively clean, choose a plate spacing of 20 mm and a plate inclination of 45'. Determine the droplet rising velocity from Stokes law as defined by equation F.4 in Appendix F.

2.

.. .. ..
3 .

VT

=

9.81 x (60 x 104)

2

x (1000 - 900)

18 x(0.8 x ~ O - ~ )
-4

vT = 2 . 4 5 ~ 10

m/s

vT = 0.245 mm/s

Determine the allowable cross sectional flow area of the plate pack to achieve a Reynolds number of 800, using equation H.6. Re = pwxqx2xx PXA

P q e H-2

SIPM Droiliiix

Mrrriiciil. EP

93-1315. Rev 1.1. N o v 1993, File I I ~ I I I I= ~ 99IiIIPLAT.DOC

Appendix H - Plate pack sizing

..

looox----8o x2x20x10-3 3600 800 =
(0.8 x 10-3) xA

Eq. H.8

..
4.

A

= 1.39 m2

To achieve the required cross-sectional area assume a plate pack of dimensions 1.2 m wide, 1.2 m high. From equation H.7 determine the required length of the plate pack.
LxA= qxx
COS( 0) X V T X F

..
..

Lx1.2x1.2=

($&) x 20 x 1 0 - ~
cos(45")x2.45x10-4 xo.9

Eq. H.9

L = 1.98m

Therefore, a plate pack of dimensions 2.0 m x 1.2 m x 1.2 m (LxWxH), 20 mm plate spacing and 45" inclination will achieve the desired separation.

H.5.

Effect of Revnolds number
We can illustrate the influence of the Reynolds number by repeating the previous calculation with a Reynolds number of 400. Steps 1. and 2. of the calculation are the same. However, in step 3., equation H.8 changes to;

..
..

400 =

1ooox- 8o x2x20x10-3 3600 (0.8 x xA

Eq. H.10

A

= 2.78 m2

Assume to satisfy this area criteria, the width and height of the plate pack are 1.4m and 2.0m respectively. Substituting into equation H.9 gives;

..
..

Lx2.Ox1.4 = L = 1.02m

( 3600 )
cos(450) x 2.45 x lo4 xo.9

Eq. H . l l

Therefore, a plate pack of dimensions 1.O m x 2.0 m x 1.4 m (LxWxH), 20 mm plate spacing and 45" inclination will achieve the desired separation. Thus, the effect of the lower Reynolds number is to require a larger plate pack cross-sectional area. However, because the velocity through the plates is lower, the length of the plates can be less to achieve the droplet separation. The volume of both plate packs is identical; Re = 800, volume = 2.0 m x 1.2 m x 1.2 m = 2.8m3 Re = 400, volume = 1.O m x 2.0 m x 1.4 m = 2.8m3 Naturally, some judgement must be applied when setting the relative dimensions of a plate pack. Very short plate lengths will not be as efficient as longer plates as the disturbances from the entrance to the plate pack will affect a larger percentage of the plate length. In most cases, mechanical, process and vessel layout requirements will restrict the allowable practical dimensions of a plate pack.

Puxe H-3

Appendix H - Plate pack sizing
H.6.
Standard Shell CPI desian
Shell has a standard design for a open, below ground, concrete based, down flow corrugated plate interceptor. This design is commonly used for land based installations. The Shell CPI design is based around a plate pack with the dimensions 1.75m x 1.OOm x 1.OOm (L x W x H). The normal capacity through the Shell design is based on a Reynolds number of 400. The design of the Shell CPI is covered in detail in the following documents. Drainage and primary treatment systems, DEP 34.14.20.31-Ger1, May 1986 Amended by Circular No.29/86, Custodian MFSH. New revision expected early 1994 (ref.2.04.1.e). De-oiling industrial waste water. Design and operation of the “CPI” (Corrugated plate interceptor) Report MF 81-8700, May 1981 Standard drawings, SIPM/SICM, 514.040 to 534.047 inclusive (Feb ai), covering general arrangements, start-up and operation, construction details, multiple bay configurations. (Included with reference MF 81-0700 above, should be updated with DEP 34.14.20.31 early 1994). These documents include example calculations, standard dimensions, and cover all civil and construction requirements for the CPI design.

PUXCH-4

SIPM Deoilirrh.Mirriuiil, EP 93-1315. Rev 1.1. Nov 1993. File

iiciine

= 99tfI!PlAT.DOC

Appendix I - Predicting hydrocyclone perJormance

1.1

Introduction
The concepts and discussions presented in this appendix are designed to introduce the user to some of the methods of characterising and predicting the performance of hydrocyclones. For more detailed information on these concepts the user is referred to the following references.

[I]
[2] [3] [4] [5]

“Comparative testing of new generation deoiling hydrocyclones”, OWTC Report, Aug 1992, EP 92-1900. “Hydrocyclones”, Svarovsky, L., Holt, Rinehart and Winston, London, 1984 ”Correlation of separation results from light dispersion hydrocyclones”, Colman, D.A., Thew, M.T., Chem Eng Res Des, Vol. 61, July 1983, Ref.2.05.l.g. “The Hydrocyclone”, Bradley, D., Pergamon press, London, 1965 “The design of hydrocyclones”, Rieterna K., KSLA report number 26986A, Oct 1956

1.2

Cut size diameter
The cut size diameter is a droplet diameter which can be used to characterise the separation performance of a hydrocyclone. A common cut size diameter definition is the 50% cut size ds0. This is defined as the hydrocarbon droplet diameter which has a 50% probability of leaving the hydrocyclone in the reject stream and a 50% probability of leaving the hydrocyclone in the water outlet stream, Le.;
if -=
nd,rej

1 , then d=d5,

nd,out

Eq. 1.1

Another commonly used cut size is ,, d , representing the hydrocarbon droplet size with a 75% chance of being removed from the water stream.

1.3

Cut size diameter correlations
Several correlations are available for the prediction of the droplet cut size. The following discussions introduce two theoretically based models and one empirical model.

1.3.1

Equilibrium orbit theory
The basis of this model is the balance between the outwardly directed centrifugal force and the inwardly s assumed directed drag and buoyancy forces acting on a hydrocarbon droplet. A droplet of a given size i to have an orbit about the centre of the hydrocyclone where all forces are in equilibrium. An important parameter is.the locus of zero vertical velocity (LZVV). This imaginary surface divides the hydrocyclone into two concentric sections, the central core where the flow is towards the reject port and the outer annulus where the flow is towards the water outlet. Hydrocarbon droplets inside the LZVV will be separated from the water and exit via the reject port. Droplets which have an orbit outside the LZVV (such as small droplets) will exit with the water stream. Using this approach, Bradley [4] derived the following expression for the cut size;
f

Eq. 1.2 The Reynolds number Rei is defined at the hydrocyclone inlet;

Appendix I - Predicting hydrocyclone perj6ormance
Rei = vi x pc x Di
PC

Eq. 1.3

This model was originally developed for narrow angle solid/liquid hydrocyclones. It should be noted that this model does not consider potentially important variables such as radial fluid flow, hindered settling effects, droplet coalescence or the effect of turbulence.

1.3.2

Residence time model
The residence time model differs from the previous model in that it assumes a non-equilibrium condition. The model considers whether a droplet will reach the centre of the hydrocyclone in the available residence time. The cut size will be the droplet size which will travel half the hydrocyclone diameter, the distance from the centre of the cyclone to the wall, in the available residence time. The radial droplet velocity is calculated from Stokes law. derived the following expression for the cut size: Rietema [5] , d ,
=0.51xDb x

[
/

Pc

\ 0.5

(Rei)1'375x Ap]

Eq. 1.4

As for the equilibrium orbit model, the residence time model does not consider potentially important variables such as radial fluid flow, hindered settling effects, droplet coalescence or the effect of turbulence.

1.3.3

Empirical model
Coleman and Thew proposed the following empirical correlations for estimating the cut size of a hydrocyclone. HY75 xDc
XPC

d 7 , =[

QxAp

]

0.5 Eq. 1.5

Where the hydrocyclone number H y , is defined by equation 1.6. The constants in this equation are determined empirically for each type of hydrocyclone. The constants given here were determined for the hydrocyclone studied in reference (31. H y , Where: c,
Cp

= c1x(Re,)'2

Eq. 1.6

= -0.15

= 0.011

The Reynolds number Re, is defined by:

Re, =

4xQxpc XXDCXPC

Eq. 1.7

1.4

Miaration probability
The separation performance or separation efficiency of a hydrocyclone can be described by the migration probability (MP). The migration probability for a droplet of diameter d is defined as the probability that it will be separated and leave the hydrocyclone in the reject stream. Pp(d)xCp x(1-R) Eq. 1.8

The reduced migration probability MP' is the migration probability independent of reject ratio, defined as; MP'(d)= 1-

(

"9"b-")xloo

Eq. 1.9

Puxe 1-2

SIPM Droilinfi Miiuiiid, EP 93-1315. Hrv 1.1, Nirv 1993. File iiriine = 99llCYCL.DOC

Appendix I - Predicting hydrocyclone pei$ormance
1.5
Empirical miaration probabilitv correlatione
For normal operating conditions, the following two correlations are available from the literature for the prediction of the migration probability. The first correlation is from Bradley [4];
MP(d)= 1-exp

[ [

-(d", --

o.l15~]]xloo

Eq. 1.10

The second correlation is from Colman and Threw ( 3 1for use in conjunction with their empirically derived cut size correlations (1.5, 1.6). The constants in this equation are determined empirically for each type of hydrocyclone. The constants given here were determined for the hydrocyclone studied in reference [3]. MP(d) = 1- exp[ cg x[ 2 - c 4

[

Where:

cg c4 c5

= -1.8 = 0.19

,"'I])(

100

Eq. 1.11

= 1.25

1.6

EmDirical pressure drop correlations
The pressure drop across a hydrocyclone can be modelled using the following power law relationship. AP = C g X (Q)'7 Eq. 1.12

where c6 and c7 are empirically derived constants. The same expression with different constants can be used for modelling both the feed-to-product stream and the feed-to-reject stream pressure drops.

1.7

Application of correlations to hvdrocvclone trials North Cormorant trials
The various cut size and migration probability correlations discussed in the preceding sections were applied to the results of the North Cormorant hydrocyclone trials (Ref. 2.5.2.h, Ref.2.5.2.i).
It was found that the Coleman and Thew correlations provided the most reasonable agreement with the experimental results.

1.7.1

1.7.2

OWTC trials
The empirical correlations of Colman and Thew (1.5, 1.6, 1.7, 1.11, 1.12) were applied to the results from the OWTC trials "Comparative testing of new generation deoiling hydrocyclones" [l]. Empirically derived values for the constants c, to c7 were determined for the Vortoil and Hydropak hydrocyclones, while constants c6 and c7 were correlated for all the tested hydrocyclone designs. The results are presented in Table 1.1
Table 1.1 Empirically derived constants to fit hydrocyclone modelling equations

c, (Feed-Product) c, (Feed-Product) c, (Feed-Reject) c7 (Feed-Reject)

0.099 1.938 0.137 2.065

0.108 2.056 0.073 2.538

0.040 2.123 0.044 2.439

0.025 2.195 0.060 2.131

SlPM Duoilinl: Mti~iiiol,EP 93-1315. Rev I . 1. Nov 199.1. File i i t i t w = 9911CYCL.DOC

Puxe 1-3

Appendix I - Predicting hydrocyclone perjormance
1.8

Nomenclature

c

d Di D ,

= = = 0 , = Hy = MP(d) = MP'(d) =

=

n

P(d) AP

Q
R

feed oil concentration (mg/l) droplet diameter (m) inlet diameter (hydrodynamical) (m) hydrocyclone body diameter (m) Vortoil nominal hydrocyclone body diameter (Db/2) hydrocyclone number (dimensionless) migration probability, the chance of a droplet with diameter d being separated (%) reduced migration probability (%) - number of droplets = volume fraction of dispersion of droplet size d = pressure drop (bar) = Volumetric flow rate (m3/h)
Qr = reject ratio R = Qf

V

Rei R e ,

P Ap

P
Subscripts

= Reynolds number at the inlet (dimensionless) = Hydrocyclone Reynolds number - fluid velocity (m/s) = density (kg/m3) = density difference between continuous and dispersed phases (kg/m3) = viscosity (kglm s)
feed stream at inlet product stream (water outlet) reject stream (hydrocarbons outlet) continuous phase

.

.

P U ~ 1-4 C

SlPM Duoiliii~ M ~ ~ i i i iEP d , 9.1-13 15, R i v 1.1. Niiv 1993. File i~iiiiic = 99IICYCL.DOC

Appendix J - Predicting levels of dissolved hydrocarbons

J.l. Introduction
The following method for the prediction of the concentration of dissolved hydrocarbons in water has been extracted from the KSLA research note:

"NAM F3 produced water clean up. Solubility and stripping of aromatics in water", P.J.F.M. De Krom, KSLA EE/4, 28th Sept 1990, Ref.3.02.2.a

5.2.

Theory
The solubility of most produced hydrocarbons in water is relatively limited. Thus a mixture of liquid hydrocarbons and water will result in the formation of two phases, each phase containing a proportion of the other phase on the basis of solubility and equilibrium considerations. Under equilibrium conditions the chemical activity (a) of a hydrocarbon component i is the same in each phase. Eq. J.l The activity of each component is defined by; a=Xxy and the distribution coefficient (m) over the two phases is described as; Eq. J.2

m=[?]

Eq. J.3

Combining equations J.l, J.2 and J.3:

m = [ ~ ]

Eq. J.4

For an ideal hydrocarbon mixture, if component i is a hydrocarbon, then the activity coefficient for component i in the hydrocarbon phase ( Y ~ , ~is ) equal to 1. For low hydrocarbon concentrations of component i in water, yj,w is virtually constant and can be taken as the same as for the pure component in water. Thus under the assumptions of ideal hydrocarbon behaviour and a low concentration of hydrocarbons in the water phase, equation J.4 simplifies to; m = y I.pure,w Substituting J.5 back into J.3, the solubility of component i in water can be expressed as; Eq. J.5

Eq. J.6

SIPM Deoi/ii~# Moiirrtrl. EP Y.Ll.315. Rrv 1.1. N m 1993. R I C I I ~ I I I I C = 99JJI)ISS.DOC

Puxe I-1

Appendix J - Predicting levels of dissolved hydrocarbons
For pure component i, Xi,h = 1, therefore;

Eq. J.7

Thus the solubility of component i from a hydrocarbon mixture can be calculated from equations J.6 and J.7 as; Eq. J.8 Therefore, the solubility of hydrocarbon i from a hydrocarbon mixture in contact with water is equal to the molar fraction of that component in the hydrocarbon phase multiplied by the solubility of the pure hydrocarbon component in water.

In practice the hydrocarbon mixture is not ideal and the activity coefficient (yi,J is greater than 1. This causes the actual solubility in pure water to typically be 20 to 30% higher than the predicted value. In addition, the effect of other variables on the solubility such as salinity, temperature, pH and the presence of production chemicals in the water phase must be considered.
Nomenclature: a c m = activity (--) = concentration (ppm(w)) = distribution coefficient (--) = mole fraction in liquid (--) = activity coefficient (--)

Y
Subscripts:

x

h = i = pure = w =

hydrocarbon phase component i of the pure component water phase

..

Comparison with experimental and field result3
The KSLA research note referenced above conducted a number of trials to compare predicted hydrocarbon solubility with experimentally determined results. Various mixtures of hydrocarbons were used, including simple mixtures of aromatic hydrocarbons to more complicated mixtures of aromatic and aliphatic hydrocarbons. The theoretical dissolved hydrocarbon concentration Ctheoretica, is determined by multiplying the molar fraction of the hydrocarbon in the hydrocarbon phase with , , C the maximum solubility of the pure hydrocarbon in water. , ,C is taken from the reference: "232 Hydrocarbon water solubility data", C.L. Yaws, Chemical Engineering, April 1990, p178-182 (Ref.3.01.2.a) A selection of , ,C , values from this source for a range of common hydrocarbons is included in Table J.4.

Table J.l contrasts the theoretically and experimentally determined dissolved hydrocarbon concentration in water for a relatively complicated mixture of aromatic compounds. Table J.2 contrasts the theoretically and experimentally determined dissolved hydrocarbon concentration in water for a mixture of aromatic and aliphatic compounds similar to that which could be expected in condensate from a gadcondensate production operation. In both tables it can be seen that the theoretically predicted dissolved hydrocarbon concentrations are lower than the experimentally determined concentrations, by 10% and 24% respectively. However, Table J.3 illustrates the predicted and measured hydrocarbon solubility for two operating gas
PUXC J-2
SIPM Droilirix Motitid. EP 9.7-1315, Rev 1 1. Niiv 199.7. File nome = 99JJDlSS.DOC

Appendix J - Predicting levels of dissolved hydrocarbons
platforms. It can be seen that there is excellent agreement between the predicted and measured results, probably as a result of the impurities present in the platform water. The hydrocarbons may be less soluble in the production water than in pure water, bringing the measured platform solubility back to the same level as the theoretically predicted solubility. Additional information on the solubility of hydrocarbons in water including data on the effect of water salinity and the use of the SRK method for phase equilibrium calculations can be found in the following reference; "API Technical Data Book Petroleum Refining, Vol II, Chapter 9 in systems containing water", 4th ed, 1982 (Ref.3.01.2.d)

-

- Phase equilibria

For guidance on the prediction of hydrocarbon solubility using simulation packages, reference should be made to; "Basic data and phase behaviour methods", DEP 20.00.1 0.1 0-Gen, April 93

J.4.

Parameters affectina solubilitv
In addition to measuring the solubility of hydrocarbons in water, the tests conducted by KSLA also investigated the impact of a number of variables on the solubility. The results are summarised in Table J.5 and are discussed below.

A "simple" mixture of aromatics was used to establish a base case solubility. The mixture was composed of 15 wt% benzene, 37 wt% toluene, 43 wt% xylene and 5 wt Yo ethylbenzene. The solubility was established as 696 ppmw at 1 atm, 25°C and a pH of 7 Effect of pH When the pH of the water was lowered to 4.5 it was found that the level of dissolved hydrocarbons in the water increased by 8% to 753 ppmw. Considering the accuracy of the experiment this variation was not considered significant. Effect of temperature When the temperature of the water was raised to 50°C it was found that the level of dissolved hydrocarbons fell by 4% to 670 ppmw. Considering the accuracy of the experiment this variation was not considered significant. Salt concentration The levels of dissolved hydrocarbons was measured for water salt concentrations of 17 g/l, 34 g/l and 51 g/l NaCI. The solubility was found to fall with increasing water salinity to 653 ppmw, 504 ppmw and 481 ppmw respectively. Presence of methanol 1000 ppmw of methanol was added to the hydrocarbon/water mixture of which 560 ppmw of the methanol dissolved in the aromatic phase. The level of dissolved hydrocarbons in the water (excluding the methanol itself) was found to increase by 40% to 974 ppmw. Presence of corrosion inhibitor When 400 ppmw of corrosion inhibitor was added to the hydrocarbon/water mixture the levels of hydrocarbons in the water phase increased dramatically by 180% to 1930 ppmw. When 30 ppmw of corrosion inhibitor was added to the hydrocarbon/water mixture the level of dissolved hydrocarbons in the water increased by 18% to 824 ppmw. However in both cases the water phase was not a clear liquid and these high levels of hydrocarbons may be a result of the formation of a stabilised emulsion of finely dispersed hydrocarbons in the presence of corrosion inhibitor and may not reflect true hydrocarbon solubility.

Appendix J - Predicting levels of dissolved hydrocarbons

Component

Molar percentage
(%)

(ppmw)

%ax

Ctheoretical

(ppmw)

%emured

Error

(ppmw)

Benzene Toluene Xylene Ethylbenzene i-propylbenzene n-propylbenzene o-ethyltoluene n-butylbenzene

11.0 23.4 23.6 3 . 0 0 . 9 2 . 1 3.7 32.2

1760.0 542.0 180.0 165.0 50.0 52.2 9 3 . 1 13.8
Totals

193.8 127.0 42.5 1.1 3 . 4 4 . 4 378
5.0 0.4

203 145 5 1 6 <2 <2 3
11

-5% -12% -17% -17%
NIA NIA NIA

-60%
-10%

4 19

Table J.2 Comparison of predicted and measured dissolved hydrocarbon contents for a mixture of aromatic and aliphatic hydrocarbons Component Molar percentage
% a x Ctheoretical %easured

Error

(PPmw)

(PPmw)

(PPmw)

Benzene Toluene Ethylbenzene Xylene i-propylbenzene n-propylbenzene o-ethyltoluene n-butylbenzene n-heptane i-octane naphthalene
I

1.6 3.4 0.4 3 . 5 0 . 1 0.3 0.5 4.7 42.9 29.2 13.3

1760.0 542.0 165.0 180.0 50.0 52.2 93.1 13.8 2.24 0.43 32.1
Totals
I

28.3 18.6 0.7 6.2 0 . 1 0.2 0 . 5 0.6 1 .o 0 . 1 4 . 3
61

44 26 1.3 8
<1 <1 <1

-36% -29% -44% -22%
NIA NIA NIA NIA NIA

<1

1 1 1

PI
79

PI

-24%

[ I ] The solubility of paraffins and naphlhalene could not be mea ired in the G c

PU#C

f-4

SIPM Deoiliiix MoiiiioI, EP 93-1315, Rev 1.1. Nov 199.3, Filr ii(liiie = 99JJDISS.DOC

Appendix J - Predicting levels of dissolved hydrocarbons

Table 5.3 Comparison between predicted and measured concentrations of dissolved hydrocarbons for actual platform production water Platform Predicted soluble aromatics (ppmw) 190 386
I I

Predicted soluble paraffins (ppmw) 2.2 1.8
I

Measured total hydrocarbons in water (ppmw) 210 380
I

Error

Platform 1 Platform2

-8.5% +2.1%

Table J.4 Hydrocarbon solubility in water at 25°C and 1 atm Formula Name M.W. Boiling point ("C) -161.5 -88.5 -42.0 -0.2 -11.6 36.1 28.0 80.1 68.8 110.6 98.4 136.0 139.1 144.3 138.3 125.6 165.1 150.7 218.0 183.3 173.7 Solubility in water (ppmw) 24.4 60.4 62.4 61.4 48.9 38.5 47.8 1760.0 13.3 542.0 2.24 165.0 174.0 221.o 202.0 0.431 52.0 50.0 93.1 0.122 32.1 13.8 0.052 iopper, J.R.,

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17' 18' 19 20 21 22 23

CH4 C2H6 C3H6 C4H10 C4H10 C5H12 C4H12 C6H6 C6H14 C7H8 C7H16 C8H10 C8H10 C8H10 C8H10 C8H18 C9H12 C9H12 C9H12 C9H20 C10H8 C10H14 C1OH22

Methane Ethane Propane n-Butane i-Butane n-Pentane i-Pentane Benzene Hexane Toluene Heptane Ethylbenzene m-Xylene @Xylene p-Xylene Octane n-Propylbenzene iPropylbenzene o-Ethyltoluene Nonane Naphthalene n-Butylbenzene Decane

16.043 30.069 44.096 58.123 58.123 72.150 72.150 78.1 13 86.177 92.140 100.203 106.167 106.167 106.167 106.167 114.230 120.194 120.194 120.194 128.257 128.173 134.221 142.284

--..---.--

Source: "Hydrocarbons: Water solubilii data", Yaws, -., Yang, H.C Hansen, K.C., Chemical Engineering,A il 1990, p177-182

* Source not identified, taken from KSLA reoort "NAM F3 DrodUCed water clean UD. Solubility and stripping of aromatics in water", 'P.J.F.M. De Krorn, KSLA EE/4, 28th Sept
1990

Appendix J - Predicting levels of dissolved hydrocarbons

Table 5.5 Results from KSLA hydrocarbon solubility trials Variable Test conditions Dissolved hydrocarbons in water (ppmw) 696 753 670 653 504 48 1 Variation from base case

Base case PH Temperature Water salinity

25%, pH=7, latm, OgA NaCl Base case + pH=4 Base case + 50°C Base case + 17 gA NaCl Base case + 34 gA NaCl Base case + 51 gA NaCl Base case + 1100 ppmw methanol Base case + 400 ppmw corrosion inhibitor Base case + 30 ppmw corrosion inhibitor

N/A
8%

-4%
-6% -28% -31% 40% 177% 18%

Methanol Corrosion inhibitor

PUKE J-6

SlPM Denilinx M i i n i d EP 93-1.715, Rev 1.1. Nov 1993, Filr ncime = 99JJDISS.DOC

Appendix K - Dissolved hydrocarbons equipment comparison

K.l.

Introduction
The comparison tables presented in this Appendix have been extracted from the following reference. “A comparison of oily water separation technologies”, Jan Dec 1992, Buss, G., Visser, R., Rye, A., Lawrence, A., SlRM report number AMGR.92.340, SIPM report number EP 93-0651. These tables have been provided to allow the user to compare the relative sizes, capital costs and operating costs of a number of alternative methods for the removal of dissolved hydrocarbons Users should be careful not to take this information out of context. The results from the comparison will be strongly influenced by the design basis and the assumptions made in equipment selection and sizing. In particular, the integration of the treatment system into the overall process will have a significant impact on the cost effectiveness of any treatment package. Factors such as the disposal or regeneration of secondary streams or the availability of utilities such as nitrogen or steam may strongly influence the suitability of a given scheme. Costs reflect 1992 prices and will naturally change with both time and technological improvements to the equipment. All the processes presented in this appendix are discussed in more detail in chapters 9 and 10.

-

K.2.

Desian basis
All equipment sizing was based on nominal water flow rates of 4.2 mVh, 42 m3/h and 420 m3/h (100 mVday, 1000 mVday and 10,000 m3/day respectively). The water was taken as contaminated with 500 mg/l of benzene with a required effluent benzene specification of 10 mg/l. The water temperature was assumed to be 35°C. With the exception of a water filter on the water feed stream, no allowance has been made for any upstream processing which may be required. Normally, upstream processing would be -required to remove the majority of the dispersed hydrocarbons and solids. Treatment or disposal of stripping streams is a parameter which must be carefully considered in the design and operation of a facility for the removal of dissolved hydrocarbons. As it is system dependent, in this comparison no consideration has been given to the treatment or disposal of stripping streams. Allowance has been included for piping, electrical, instrument and structural bulks. Specific inclusions and exclusions for each system are documented below. Air stripping: Nitrogen stripping: Simple atmospheric air stripping column. Includes column, water feed pump, air blower, water filter and column packing. Similar to air stripping column. Includes a capital cost for a nitrogen generation plant. Includes column, water feed pump, water filter and column packing. Based on recompression of the stripping gas to circa 65 barg. Includes column, water feed pump, water filter, column packing and suitable multiple stage compression system with associated coolers and scrubbers. Assumes an external source of steam is available for use in the stripping column. Allowance is made for the column, water feed pump, water filter, column packing, overheads condenser, reflux drum and feed preheater. Uses a reboiler to produce steam from the product water stream. The system is designed to operate under vacuum to improve the stripping and lower the boiling temperature, Allowance is made for the column, water feed pump, water filter, overheads condenser and reflux drum, feed preheater, reboiler,

Gas stripping:

Open steam stripping:

Closed steam stripping:

SIPM Deoiliitl: Mcrriiirrl, EP Y3-131.5. Krv 1.I , N w 109.t. R I i , r i i i ~ i i c ’= YYKKCOMP.DOC

Puxe K-I

Appendix K - Dissolved hydrocarbons equipment comparison
vacuum pump and water discharge pump. Pervaporation: Pervaporation is a separation process combining distillation with membrane separation of the vapour. The process has been investigated by KSLA, both for removal of dissolved hydrocarbons and the regeneration of glycols. Allowance has been made for the water feed pump, water filter, membrane system, preheater, reboiler, overheads condenser and reflux drum. Based on the use of the SDI Extran membrane. Sizing information was provided by the vendor. For the test case the membrane will not achieve 10 mg/l in the outlet water without dispersed hydrocarbons being present in the feed. The user is referred to Section 8.17 and Appendix L for a more complete discussion of the advantages and disadvantages of membrane systems. In a airlift bioreactor the biomass is attached as a film to suspended carrier particles, allowing a reduction in bioreactor size compared to conventional systems. The process has been investigated by KSLA. Allowance is made for the reactor vessel, nutrient storage tank, nutrient dosing pump and water feed pump. No allowance is made for the supply of compressed air to provide the air lift circulation. Based on the co-current stripping of hydrocarbons from water using kerosene, using in-line mixers for co-current contacting and hydrocyclones for phase separation. The process is being investigated by KSLA. Allowance is made for two in-line mixers, two phase separation hydrocyclones, water feed pump, lean kerosene pump and kerosene recycle pump. However no allowance is made for the regeneration or disposal of the rich kerosene.

Nanofiltration:

Airlift bioreactor:

Solvent stripping:

K.3.

Results
The capital costs, operating costs, weights and power consumptions of the different equipment configurations, based on the assumptions and definitions outlined above is presented in the following tables.
Table K.l Capital costs of equipment for the removal of dissolved hydrocarbons (US$, Jan 1992) Process Water flow rate (m3/h) 42 I

4.2

I

420

Air stripping Nitrogen stripping Gas stripping Open steam stripping Closed steam stripping Pervaporation Nanofittratiin Airlift biotreater Solvent stripping

150,000 540,000 380,000 240,000 350,000 430,000 400,000 237,000 260,000

________________
2,000,000 970,000

210,000 1,270,000 1,110,000 480,000 500,000 1,470,000

1,120,000 4,750,000 4,490,000 2,500,000 2,900,000 12,300,000 10,000,000 15,500,000 2,950,000

Puxe K-2

SlPM Dciiiliiig Mioiuol. Ef' 93-13l.7. Kuv 1. I . Nov 1992. Filr

ii~ine =

99KKCOMP.DOC

Appendix K - Dissolved hydrocarbons equipment comparison

Table K.2 Annual operating costs of equipment for the removal of dissolved hydrocarbons (excludes energy costs) (UWyear, Jan 1992) Process Air stripping Nitrogen stripping Gas stripping Open steam stripping Closed steam stripping Pervaporation Nanofiltration Airlifl biotreater Solvent stripping
1.

7-p+
23,000 80,000 60,000 36,000 52,000 80,000 70,000 36,000 40,000 32,000 190,000 170,000 73,000 75,000 370,000 300,000 150,000

Water flow rate n h)

420

-_________-_____

Source: 'A comparison of water separation technologies", In - Dec 1992, Buss, G., Visser, R., Rye, I Lawrence, A,, SlRM report number AMGR.92.340, SlPM report number EP 93-1

170,000 670,000 7 10,000 440,000 440,000 3,300,000 3,000,000 2,300,000 440,000

Process Dry Air stripping Nitrogen stripping Gas stripping Open steam stripping Closed steam stripping Pervaporation Nanofiltration Airlifl biotreater Solvent stripping

4.2

Wet

Water flow rate (m3/h) 42 Dry Wet

Dry

420

Wet

10 10 2 1 20 1 9 18 20 10 7.9

15 14 26 25 24 2 1 22 19 8 . 1

__-_55 34

13 1 2 76 30 28 26

-----

23 2 1 85 38 37 30

'

140 35

70 77 215 170 170 163 150 400 124

186 170 275 260 260 210 200 1,300 130

SIPM Dwf11tfg Mof~riol. &P 93-1315. Rrv I I . N ~ 1993. V File ii(iiife = 99KKCOMP DOC

Puge K-3

Appendix K - Dissolved hydrocarbons equipment comparison

Table K.4 Power requirements of equipment for the removal of dissolved hydrocarbons (kW) Process Air stripping Nitrogen stripping Gas stripping Open steam stripping ( 1O O O C ) Closed steam stripping (35°C) Pervaporation (35°C) Nanofiltration Airlift biotreater Solvent stripping

e
4.2 5
4

- 42

11

420

Comments Excludes: Further VOC and water treatment

112 Includes: Air blower and feed pump electricity 37

6 256 780 760 760

34
82
84
84
Note

Includes: Blower and feed pump electricity Excludes: Further VOC and water treatment, nitrogen generation 1,520 Includes: Pump and compressor electricity Excludes: Further water treatment

7,780 Includes: Electricity and steam 7,550 Includes: Electricity and steam 7,550 Includes: Electricity and steam

Excludes: Further water treatment Excludes: Further water treatment

Excludes: Further water treatment

Jote 1 Note 1 No further treatment required

1 . 5 22

2
176

6

Includes: Pump electricity Excludes: Water pre-treatment Excludes:Treatment of solvent

542 Includes: Pump electricity
I

1. Power reauirements similar to air sti 2. VOC = Volatile organic compounds 3. Source: 'A comparison of oily water separation technologies", Jan Dec 1992, Buss, G.,Visser, R., Rye. A., Lawrence, A,, SlRM report number AMGR.92.340, SlPM report number EP 93-0651

-

Puxe K-4

SlPM Deoiliii~: Miriiriirl, EP 93-131S. Rrv 1.1, Nuv 1993. Filr

iiiiiiir

= 99KKCOMP.DOC

Appendix L - Membrane trials

.

. .

. .

..... .

...

. .

L.l.

Introduction
The discussions in the following sections give a brief summary of the commercially available membranes that have been recently tested by Shell though Opco or OWTC trials. The majority of the information has been taken from the following two OWTC trials: "Membrane filter trials with various oily waters at Orkney Water Test Centre Ltd, Phase I , 15 April 1991. EP-no. 91-1017 Four membranes were examined in the Phase I trials: Alcoa Petrolox, SDI, Stork-Wafilin and X-Flow. The report investigated the effect of the following variables on the performance of the membrane systems: Variation in oil type, concentration, droplet size and slugs of oil. Variation in water temperature and salinity. The effect of oil field chemicals, gas breakout, and scale forming compounds.
0

"Membrane filter trials with various oily waters at Orkney Water Test Centre Ltd", Phase II, 20 September 1991, EP-no. 91-2152 Three membranes were examined in the Phase II trials: WL Gore, Schelde Delta and SDI (modified since Phase I trials). The report investigated the effect of the following variables on the performance of the membrane systems: Variation in oil type, oil droplet size and slugs of oil. Variation in water temperature and salinity. The effect of oil field chemicals and scale forming compounds. The report also investigated the performance of the Wemco Silver Band crushed nut shell deep bed media filter.

However the membranes discussed in this appendix do not represent the complete range of membranes that could potentially be used for the removal of dispersed hydrocarbons from water. Reference 2.15.1 .h from the bibliography contains a listing of other membrane manufacturers who are potentially involved with the production of membranes for waste water treatment.

L.2.

Alcoa Petrolox
The Petrolox system is a packaged unit containing Alcoa Membralox membrane elements. The Membralox elements are made from alumina and shaped as hexagonal prisms with flow channels running through the element. The bulk of the element is supporting substrate, however the inner surface of the channels has a thin ceramic layer with the desired pore size. This thin layer acts as the membrane. A range of pore sizes are available from 0.2 pm to 12 pm (12 pm = substrate only). A 0.8 pm pore size is usually used for deoiling duties. The filter is automatically cleaned every 2 to 6 minutes by sending a back-pulse of clean permeate through the system for a duration of 0.5 to 2.0 seconds. This helps dislodge accumulated hydrocarbons and solids from the surface of the membrane so they may be carried away. Dosing of ferric chloride and sodium carbonate in the oily water feed is used to improve the flux and life of the membrane by precipitating fine solids to act as a filter aid. Dosing requirements can be reduced if suspended solids are present in the feed stream. When the flux declines to unacceptable levels the membrane can be chemically cleaned. The alumina structure allows a wide range of chemical cleaning agents to be used. The Alcoa Petrolox system has been tested at the OWTC, achieving a permeate quality of 1 to 29 mg/l of hydrocarbons with a typical level of 10 mg/l. Permeate quality was higher for heavier oils (2 mg/l for 21" API oil). Chemical cleaning was effective with the unit returning to a "clean" condition. Testing was also conducted at Nam with similar results to the OWTC.

A number of trials of the Petrolox system have been conducted in the USA and two 1000 m3/d full scale units have been installed. These have indicated that the system can achieve hydrocarbon levels below 5 mg/l, however the installations require a significant amount of operator attention to achieve reliable performance. Fouling has been variable. The potential impact of recycling hydrocarbon concentrate must be evaluated as the recycle stream will contain the precipitated ferric chloride which may affect the stability of oil/water emulsions.

Appendix L - Membrane trials
L.3.

SDI Extran
The Separation Dynamics Inc (SDI) system uses the cellulose based Extran membrane. This membrane is a non porous type, fashioned in the form of hollow fibres. The fibres are collected into bundles and packaged into pressure vessels. The oily water feed flows through the inside of the fibres with water diffusing through the membrane to the outside of the fibres for collection. Because the membrane does not contain pores it is claimed to be quite resistant to fouling. However as the flux rate through the membrane is governed by diffusion, the flux rate per unit area of membrane is relatively low, in the order of 30 times lower than the porous ceramic membranes. The SDI Extran system has been tested at the OWTC, achieving a permeate quality of 4 to 30 mg/l of hydrocarbons with a typical level of 10 mg/l.
A recent trial of the SDI system by Expro (Ref.2.15.2.f) demonstrated that dispersed hydrocarbons in the order of 1000 to 20,000 mgA were reduced to 10 5 5 mg/l. Dissolved aromatics in the order of 700 to 7000 mg/l were reduced to 300 rt 50 mg/l, though the extraction effect of the concentrated dispersed hydrocarbons is thought to be the dominant influence on the removal of dissolved hydrocarbons. Only slight fouling was observed.

L.4.

X-Flow
The X-Flow membrane is a polyethersulphone capillary tube membrane of 0.2 pm pore size. The system is designed for automatic backflush and chemical cleaning. The X-flow system was tested at the OWTC, achieving a permeate quality of 1 to 18 mg/l of hydrocarbons with a typical level of 8 mg/l. One X-Flow membrane tested had an adverse reaction with corrosion inhibitor, though this was corrected with a modified membrane. Fouling was experienced using the 1.0 mm capillary membranes, through better results were obtained with the 1.5 mm membranes. In operation the flux declined to 50% of the rated flux rate. The X-flow system has also been tested by M a s k , obtaining low levels of hydrocarbons in the permeate. However operation problems were experienced with fouling and degradation of the membrane material.

L.5.

Stor k-Waf iIin
Stork-Wafilin manufacture a range of membranes including ceramic microfiltration membranes, polymeric capillary microfiltration membranes and tubular polymeric membranes. Tests at NAM indicated that the best overall results were obtained using the tubular polymeric membranes. Although higher initial flux rates were obtained with more open membranes, these tended to foul more rapidly. The Stork tubular membrane was tested at the OWTC, achieving a permeate quality of 1 to 20 mg/l of hydrocarbons with a typical level of 8 mg/l. However flux rates were variable and did not reach a stable value. The Stork system was tested in 1988 on an Dutch Mobil platform with good hydrocarbon removal performance, but operation problems were experienced with gradual fouling.

L.6.

Schelde-Delta
The Schelde-Delta membrane system is a ceramic alumina membrane on a silicon carbide support medium. Tests at the OWTC indicated a permeate quality of 13 to 68 mg/l with a typical level of 20 mg/l. The performance of the system was significantly upset by the presence of corrosion inhibitor and demulsifier.

L.7.

WL Gore
The WL Gore design uses a tubular expanded PFTE oleophilic membrane. Tests at the OWTC indicated a permeate quality of 6 to 30 mg/l with a typical level of 11 mg/l. Flux rates declined to 20 % of the rated flux rate.

L.8.

Hoouovens
The Hoogovens design uses an alumina ceramic membrane. The system was tested by NAM (as a simple trial unit) with encouraging results. However, further testing with a more complete packaged unit gave variable results with permeate quality in the order of 40 mg/l.

P q e L-2

SIPM Drri;liii~ Monrrrd. Et' 93-1315, Rev 1.1, Niiw 1993, Fi/r iwnr = 99LLMEMB.DOC

Amendix L - Membrane trials
L.9. Zenon
A number of Zenon ultrafiltration membranes were tested in 1990 at two sites in Canada for the removal of hydrocarbons from produced water, one site (site "A") being the Shell Canada Peace River development. Typical performance was a reduction in oil content from 2000 mg/l to 100 mg/l at site "A" and the reduction in oil content from 1000 mg/l to 30 mg/l at site "B".The membrane was found to remove essentially all the dispersed oil and suspended particles and in the order of 20% of the dissolved hydrocarbons from the water. However large flux deviations were noted for all membranes tested as a result of decreasing productivity due to fouling and the need for frequent cleaning. Long term flux rates continued to decline even after cleaning, indicating the gradual permanent fouling of the membrane. Average flux rates achieved during the trial were considered to be high enough to make the technology competitive with more conventional alternatives such as flotation combined with deep bed media filtration. However, due to the gradual fouling of the membrane there is doubt over what flux rate could be expected after long term operation and as a result further development is required to enable stable long term flux rates to be maintained.

Appendix L - Membrane trials

P U , ,

L-4

SIPM Dwi/;iix Mtriiutil. Et’ 93-1315, Rev 1.1. Nov 1993. File iitiriie = 9YLLMEMB.DOC

Bibliography

. . . . . . . . .

1.

Introduction
The following bibliography lists the sources of information used in the update from the SlPM Dehydration/Deoiling Manual EP 89-0150 to this Deoiling Manual. All referenced information has been archived at SlPM EPD/42 and can be requested if not available from local sources.

2.

Literature searches
Literature searches have been made on the SlPM Stairs database to identify internal reports and papers relevant to deoiling. The following keyword combinations were used for the literature search. water

AND

treatment

(peg manual) (oily oily
0

AND

water$

AND epr NOT

(treatment watertreatment) (treatment watertreatment)

AND water) AND waters

deoiling

AND

epr

NOT

Q water) (produced &
oil

AND

epr

AND

(injection disposal)

NOT

(treatment watertreatment)

0

ADJ in ADJ

(water waters)

AND

epr

NOT

(treatment watertreatment)

caisson$

3.

Index
All the references in the Bibliography include a short description of the reference and an identifying reference number.
The references are grouped in numerical order. As each topic has a unique reference number, all the references on a given topic will be grouped together. For example, all references to hydrocyclones are grouped together under the reference number 2.05.X.X. The following table presents an index to the topics included in the Bibliography.

INDEX TO BIBLIOGRAPHY
1. GENERAL
1.1........Produced water analyses, legislation 1.2 ........ Water analysis methods 8 standards 1.3 ........ Oil-in-wateranalysers Size particle analysers 1.4 ........ 1.5........ Treatment chemicals 1.6 ........ Ballast waters Sampling 1.7........ 1.8........ Emulsions 2. DISPERSED HYDROCARBONS

2.12 ...... Pre-coat filtration 2.13 ...... Cartridge filtration 2.14 ......Coalescers 2.15 ...... Membranes 3. DISSOLVED HYDROCARBONS 3.1 ........Dissolved hydrocarbons .General 3.2 ........Stripping 3.3 ........Biologicaltreatment 3.4 ........Carbon adsorption 3.5 ........ Solvent extraction 3.99 ......New technologies
OTHER INFORMATION

2.1 ........Dispersed hydrocarbons - General 2.2 ........Inducedgas flotation 2.3 ........API separators 2.4 ....... Plate packs 2.5 ........ Hydrocyclones 2.6 ........Skim tanks 2.7 ........Deep bed filtration 2.8 ........Centrifuges 2.9 .......Dissolved gas flotation 2.1 0 ......Caissons 2.1 1......Rotary cyclones

4.1 .......Heavy metals 9.0 ........Vendor equipment manuals and brochures
OWTC TRIALS

3iven reference prefix of Ref.OWTC, listed at end of Bibliography

Bib1iograp hy

BIBLIOGRAPHY

- REFERENCE LISTING
DESCRIPTION OF REFERENCE

REFERENCE TITLE
Characteristics of Production Waters, Merville, E.de, Presented at the Regional Seminar on Technical Aspects of Oily Water Discharges, Bahrain, Nov 1982, The Oil lndustry lnfernational Exploration & Production Forum The composition of produced water from Shell operated oil and gas production in the North Sea, Jacobs, R.P.W.M., Grant, R.O.H., Kwant, J, Marquenie, J.M., Mentzer, E., lnfernational produced wafer symposium, Feb 4-7, 1992, San Diego Characterisation of residual hydrocarbons in produced water discharged lrom gas production platforms, Callaghan, D, Baumgartner, W., Society of Petroleum Engineers paper, SPE 20881 Environmental effect of produced water from North Sea Oil operations, Someiville, H.J., Bennett,D., Davenport, J.N., Holt, M.S., Lynes, A., Mahieu, A., McCourt, B., Parker, J.G., Stephenson, R.R., Watkinson, R.J., Wilkinson. I.G., Marine Pollution Bulletin. VollB/Nurnber IO,Oct 1987 A comprehensive determination of produced water composition, Tibbets, P.J.C., Buchanan, I.T., Gawel, L.J., Large, R., lnternationalproduced wafer symposium, Feb 4-7, 1992, San Diego Characterisation of produced water discharges, Conoco presentation, 14/1/9 1 Waste management programme -Analysis of North Sea overboard water discharges, Lynes, A,, McCourt, C.B., Thornton Research Centre, April 1991, TNGR.91.014, ep-no.91-0832 A survey of produced water studies, Stephenson, M.T., lntemationalproduced wafer symposium, Feb 4-7. 1992, San Diepo Shell Expro's Wastes 1989 Recommended practices for the monitoring and recording of effluents and wastes in E&P operations, Oct 89, Report EP 892460 Characteristics of refinery wastes, extracted from API Manual on Disposal Of Refinery Wastes, Chap 13 Section 1. Information in water pollution, extracted from API Manual on Disposal Of Refinety Wastes, Chap 2 Components of produced water: A compilation of industry studies, Stephenson, M.T., Journal of Petroleum Technology, May 1992 Environmentalaspects of platlorm discharges: Part II Monitoring of inorganic discharges lrom Brent and Dunlin platforms, McCourt, C.B., TNOR.86.035, EP 86-1136, Dec 86 Waste management programme Analysis of North Sea overboard discharges Part 2, Lynes, A., McCourt, C.B., Thornton Research Centre, March 1992, TNGR.92.045, epno.92-0727 The environmental impact of refinery effluents, Concawe's assessment, Concawe report 1/80, Feb 1980

Reference
number
Ref.l.Ol.1.a

Discusses the distinguishing characteristics of production waters. Basis for tables presented in chapter 2 discussing the relative contributions of dissolved, dispersed and polar hydrocarbons in water. Discusses the characteristics of water discharges lrom gas platforms, relative amounts of dissolved and dispersed hydrocarbons, droplet size distributions, effect of corrosion inhibitor. Written by Shell personnel, discusses the composition of the water effluent discharges from a number of North Sea platforms, the toxicity of the effluents as measured in the laboratory and in the environment and the dispersion characteristics of the effluent in the ocean. Discusses the methods used to identify 5 groups of characteristics of effluent water from several North Sea platforms, 1) Physical parameters, 2) Petroleum hydrocarbons, 3) Minerals, salts and metals, 4) Non hydrocarbon organics, 5) Treatment chemicals. Presentation covering the work and results of characterising produced water discharges lrom Murchison and Hutton platforms. Delves into analytical methods and treatment chemicals. Gives the analysis 01 the effluent streams from the Expro North Sea platforms, including organics and heavy metals. Claims there are significantly more treatment chemicals being used. Relatively simple discussion collecting the results of a number of oily water surveys together. Detailed report quantifying and discussing all waste streams from Shell Expro for 1989. Covers the grading 01 various materials in terms of toxicity and the general practices that should be followed for monitoring all effluents. Discusses the characterisation of waste waters such as various oxygen demands, typical contaminants, heavy metals, temperatures etc. Discusses the environmental impacts 01 waste waters including oxygen content, turbidity, pH, oil concentration, Discusses the contaminants present in produced waters including hydrocarbons, heavy metals, radionuclides, and treatment chemicals. Also discusses the potential environmental effects of these chemicals, Results lrom a sampling and analysis program. Furthers part I work (1.Ol.l.g) in identilying unknown organic material as naturally occurring humic acids. Discusses the range of contaminants in refinery discharge water in Europe and discusses the potential environmental impacts. Discussion on the problems faced when meeting effluent limits lrom gas platforms, Document not referenced. Unrelerenced discussion of the NOGEPA view on water discharges. Discussion on the magnitude and distribution Of various sources of pollution in the North Sea. Discusses the history of the Parcom standard, its current implementation and the development of uniform standards for its application. Discuses a range of water standards lrom drinking water to 1 water for industrial use. Only useful as background information. Discusses the introduction of the new 29 mg/l discharge levels in the USA. Comments that the new levels are based on the expected performance lrom improved induced gas flotation

Ref.l.Ol.1.b

Ref. 1.01.1 .c

Ref.l.Ol.1.d

Ref.l.Ol.1.e

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Ref.1.Ol.l.g Ref.l.01 .l.h Ref.l.01 .l.i Rel.l.01.1.j Ref.l.01.1 .k Ref.l.01 .l .I Ref.l.01 .I .m

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Ref.l.01 .l.n 3ef.l.01 .l.o

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3ef.l.Ol.l.p 3ef.l.01.2.a 3el.l.01.2.b 3ef.l.01.2.c 3ef.l.01.2.d ?ef.l.O1.2.e W.1.01.2.f

Production water from gas/condensate platforms, Discussion on limits lor oil content, 1st draft, 1986, Not referenced Water discharged from offshore platforms, The NOGEPA view, Not referenced Oily water discharges from offshore North Sea installations: A perspective, Read, A.D., Blackman, R.A.A., Marine Pollution Bulletin, Vol.11, pp 44-47 The origin and development of the PARCOM provisional target standard, Read, A.D., E & P Forum report 2.43143, Dec 1987 United Kingdom water quality standards arising from European community directives, Gardiner. J.. Mance, G.. Julv 1984 New produced water guidelines to impact U.S. operations significantly, Bell, S., Petroleum Engineer International, May 1993.

Pu,qe Biblio~,qruphy-2

SIPM Deoiliiih.Miiiiiiiil, EP 9.1-131S. Rev 1.1.NIIV1993. Fik nrriiie = YYZZBIB.DOC

Bibliography
A protocol for determining oil and grease in produced waters, Simms, K., Zaidi, A., Bhargava, O., lnternationalproduced water symposium, Feb 4-7, 1992, San Diego On-site testing of oilfield waters, Robinson,K, Society of Petroleum Engineers, Paper SPE 14128, 1986 PD Oman oil-in-water measurements, Bannell, J., Personal communication Norwegian standard for oil in water analysis, NS 4753, unofficial English resume DIN 38 409 Part 18: German standard methods for the analysis of water, waste water and sludge, Determination of hydrocakons Determination of hydrocarbons in aqueous effluents from the oil industw by infrared analysis, Concawe report 1/84 NEN 6675: Water Bepaling van he1 gehalte aan minerale olie Oct 1989 met behulp van infrarood-spectrofotometrie, (Water Determination of mineral oil content by infrared spectrophotometry) Measurement of oil in effluent water discharged from Shell Expro platforms. A review of sampling and analysis methods, Booth, S., Well engineering information note WEIN/3269, 15/6/92 Good discussion on the limitations of current analysis procedures and the search for a suitable replacement to Freon 113 Written by Oil Plus, discusses the methods used for analysis of oil field waters, including sampling, solids, particle sizing, core tests, scale and corrosion inhibition Recommends the use of mgA as the unit for measuring oil in water over the use of ppm. Also discusses in general terms various aspects of measuring oil in water levels. Unofficial translation from Norwegian into English. Resume only German standard for measurement of hydrocarbons in water. Excellent text covering most aspects of measuring oil in water, including tables of all the existing methods etc. Dutch standard for measuring oil in water, published Oct 1989 Ref.l.02.l.a Ref.l.02.l.b Ref.1.02.l.c Ref.l.02.1 .d Ref.l.02.l.e Aef.1.02.1.f Ref.l.OP.1.g

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Methods of analysis and sampling of oil in water, Oldham, G.F., E B P Forum report 2.33/115,1985 Determination of Total Hydrocarbons in Water, Rotteri, S. Concawe article, presented as the Workshop on the Chemistry and Analysis of Hydrocarbons in the Environment, Barcelona, Nov 81 How to improve the accuracy in the EPA static sheen test, Weintritt, D.J., Qaisieh, N.S.. Otto. G.H., Oil and aas journal API recommended practice for analysis of oil field waters, API RP 45, JUIV 1981 Analysis of trace elements (heavy metals) in produced water, Personal communication from KSLA Environmental monitoring of trace elements in water discharged from oil production platforms, McCourt, C.B., Peers, D.M., Petroanalysis'87, Edited by Crump, G.B., 1988 John Wiley & Sons Environmental aspects of platform discharges: Part 1 Development of an analytical methodology for analysis of inorganics in production waters, Williams, G., McCourt, C.B., TNOR.85.023, EP 06-3621, Sept 85 633 organic chemicals: Surface tension data. Chemical Engineering, March 1991 Oil in water on line analysers, A survey of operating experience in the oil exploration and production industry, E & P Forum report, 2.27/109, Oct 85 An on-line method for the detection and measurement of oil in water discharges, Bannell, J.L., van Deelen. C., KSEPL, prepared for the 1992 Production and process technology conference, The Haque, Oct 1992 Laboratory evaluation of the Baird Petrolarm oil-in-water monitor, Willigers, M.C., der Kinderen, W.J.G.J.. Nov 88, KSEPL RKOR.88.027, EP 88-2562 Laboratory investigation of the AEG-Oili-Si000 Mark C oil-inwater monitor, Williaers. - . M.C... KSEPL RKGT.90.115. EP 903029. Short evaluation of the Horiba OCMA 25 oil-in-water monitor, Scheers, A.M., KSEPL RKER.84.133, EP 61044, May 84

Reviews the water sampling and measurement procedures at all Expro platforms, also a brief description of the water treatment facilities on each platform. Recommends moving to IR analysis and better sample points. Discusses practical problems in sampling and analysis Brief paper summarising the basics of the infrared analysis procedures Discusses the EPA sheen test used in the USA for assessing the level of hvdrocarbons in drilling muds and wastes. Covers a range of procedures for most common production water analyses. Brief covers recommendations for sampling and presetvation of samples containing heavy metals Discussion into the methods and analysis techniques used for the monitoring of trace elements from the Shell Expro platforms. Discusses the techniques required for sampling, preservation and analysing discharge waters. Data and methods for the prediction of surface tension. Discusses the application and problems experienced with monitors in the field Discusses the current KSEPL development of a oil in water monitor utilising short wavelength infra red light. Presents encouraging results and work is continuing. Test of a UV fluorescence based monitor. The test was not considered successful. Meter gave good results for measuring oil concentration, however was too sensitive to chanaes in water temDerature and not built to suitable industrial iandards. Considered the instrument to give good results. Not sensitive to aromatics. Some modifications required to exclude solids to extend the service life of the filters. Numerical investigation into the use of determining particle size distributions by optical density measurements

Ref.l.OZ.1.h

Ref.i.02.1 .i Ref.l.02.l.j

Ref.l.02.1 .k Ref.1.02.2.a Ref.1.02.2.b Ref.l.02.2.c

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Ref.l.02.2.d

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Ref.1.03.2.a Ref.l.03.2.b

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Ref.l.03.2.c Ref. 1.04.1 .a

Characterisation of particle suspensions by spectral extinction: A numerical study, Wilkinson, D.. Waldie, B., Powder technology, 68 (1991) pp 109-115 Laser particle sizing, Butcher, C., The Chemical Engineer, 11 Oct 1990, p 34 Droplet size distribution analysis with an image-analysis system, Oil/waler separation, (1989-1 990), Molenaar, H.J., Fens, T.W., Bonnie, J.H.M., AMGR.90.108, EP-No.90-2982 The use of on-line optical devices for measuring oil in water content, Colman, D.A., Thew, M.T., International conference on Optical Techniques in Process Control, The Hague, June 1983 Galai CIS-1000 test report, H.P. Visser, R.M. Visser, AMGR.93.274 Vortoil DlOO Analyser and Galai CIS-1000 Opus particle size analyser, Opus UK Chemical Notification Scheme, 1993

Short discussion of the use of lasers and optical methods for particle size analysis. Discusses the KSLA method of determining droplet size ,distribution using the process of microphotography and computer assisted image analysis. Discusses the successful use of the Oilcon meters for measuring oil content from the discharge of a hydrocyclone. KSLA test of the Galai particle size analyser. Performance was generally good but operating envelope of instrument needs better definition. Galai brochures. Preliminary information for Vortoil for oil measurements. Also Fax from Vortoil confirming 80 barg design pressure, soon to be increased to 120 barg. Brochures on ultrasonic particle size analyser, could potentially be used for on-line particle size measurement of water in oil as medium does not have to be transparent. Presents the method used to categorise process chemicals used in the UK production industry and gives a guide to their

Ref.l.04.2.a Ref.1.04.2.b Ref.l.04.3.1 Ref.1.04.3.2 R~f.1.05.1 .a

SlPM Droiliiil: Mioiirril. EP 93-1315. K r v I . 1.

Noli

IY9.7. Filr

I I I ~ I I I= Y

99ZZ111Il.I~OC

Puac Oibliogrupliy-3

Chemical treatments and usage in offshore oil and gas production systems, Hudgins Jr, C.M., Journal of Petroleum Technology, May 1992, Review of speciality chemicals used for the treatment of produced fluids, van Laar, H.G., SIPM, EP-53975, not dated Desianina and selectina demulsifiers for ootimum field perfcirmaice based on production fluid characteristics, Berger, P.D., Hsu, C., Arendell, J.P., Sociefy of Petroleum Engineers, SPE 16285, 1987 Improved demulsifier chemistry: A novel approach in the dehydration of crude oil, Staiss, F., Bohm, R.. Kupfer, R., SPE Production engineering, Auq 1991 Deoiling chemicals for crude oil-in-water emulsions, Mitchell, R.W.. A u 1973, ~ EP 04-5055 Standard practice for coagulation-flocculation jar test of water, ASTM D 2035-80 Surfactants: Super molecules, Samdani, G., Chemical Engineering, March 1991 Flotation aid composition and method of use thereof, US Patent 5,151,195, Sept 1992, Petrolite Corporation List of suppliers of oil field chemicals, April 93 Welchem deoiler field trials in Marmul (MMPS), Report BDD/166/92, McKay, A,, June 92 A laboratory investigation 01 corrosion inhibitors for gas production, Glendinning. D., SPC/2, March 1989, NAM The tanker industry in the 199Os, Shell Briefing Service, Number 5 1991 Ballast water. Extract from API Handbook on Refinery Wastes, Chapter 7 Environmentalaspects of the gravity based structure F3-FB, Aarts, J.L.J., June 89, NAM Report 16.813 Sampling of liquid effluents from refineries, Concawe report, July 1980, Report no 7/80 Slandard practice for manual sampling of petroleum and petroleum products, ASTM D 4057-88 Standard practice for automatic sampling of petroleum and petroleum products, ASTM D 4177-82 On-line process stream analysis Sample take-off and transportation, Shell DEP 32.31.50.10-Gen, March 1992 Measurement of oil in effluent water discharged from Shell Expro platforms. A review of sampling and analysis methods, Booth, S., Well engineering information note WEINl3269. 15/6/92

Discusses treatment chemicals typically used offshore and their potential environmental impacts. Discussion covering all commonly used types of treatment chemicals. No date given but suspected to be pre 1986 Discusses the basic principles behind the function and selection of demulsifiers for Crude oil dehydration. Discusses development of new polyester amine demulsifiers which are claimed to have better performance than existing demulsifiers. Good discussion on the use of deoilers, however report is relatively old. ASTM Standard General discussion on new types of surfactants Patent application concerning novel chemical compositions useful as a filter aid. Discusses the use and mechanism of such aids in flotation systems. As forwarded to Hocal Discusses some theory and field trials of the use of deoiling chemicals with IGF, FWKO and a Hydromation filter. Discusses the testing of emulsion forming characteristics of several corrosion inhibitors for gas operations. Finds some are better at not stabilising emulsions than others and recommends field trials with the best chemicals from the tests. Discusses the tanker industry and the use of double skin hulls, segregated ballast Discusses the requirements for a ballast water treatment system suitable for a land based terminal. Discusses the levels of contamination expected in the ballast water from a proposed GBS (includes calculations) Discusses a wide range of aspects associated with sampling including isokinetic sampling, sampling solids and automatic samplers ASTM Standard ASTM Standard Shell DEP for sample points for on line analysers Reviews the water sampling and measurement procedures at all Expro platforms, also a brief description of the water treatment facilities on each. Recommends moving to IR analysis and better sample points. Discusses the specifications and use of the KSEPL transparent sampling bottle ASTM Standard ASTM Standard ASTM Standard Discusses the errors introduced when sampling slurries from the pipe wall. Indicated that velocities higher than the isokinetic velocity may be preferable. However, also showed that error was lower for smaller particles with less inertia. Investigation of sampling errors arising from sampling slurries using a probe. Illustrates the influence of some aspects of the probe design. Discusses the sample points used by Expro, particularly those used on North Cormorant for measuring droplet size distributions. Recent SlPM guidelines discussing alliorms of sampling: Tends to refer to existing Dehydration and Deoiling manual for sampling of water streams, but contains some useful information and guidelines. Illustrates typical simple probe designs and recommends samples are taken at least D/3 away from pipe wall. Also discusses sample containers. Similar to 1.07.1 .n above, applies to automatic sampler designs.~~ Extract from report AMTR.88.002
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Ref.1.05.1 .b Ref.l.05.1 .c Ref.l.05.2.a

Ref.l.05.2.c Ref.l.05.3.a Ref.l.05.3.b Ref.1.05.3.c Ref.1.05.3.d Ref.1.05.4.a Ref.1.05.5.a Ref.1.05.6.a

Ref.l.06.1 .a Ref.1.06.l.b Ref.l.06.2.a Ref.l.07.l.a Ref.l.07.1 .b Ref.l.07.1 .c Ref.1.07.1 .d Ref.1.07.1 .e

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Instruction manual, Transparent pressure sampling bottle for online stability tests of oiVwater mixtures in production systems, Aug 1985, Mandersloot, W.A.J., Stadt, M.E. van de, KSEPL RKMR.85.012, EP no. 6391 1 Standard Practices for Samplina of Waterborne Oils, ASTM D 4489-85 (Reapproved 1990) Standard Practices for Sampling Water, ASTM D 3370-82 Standard Specification for Equipment for Sampling Water and Slream, ASTM D 1192-70 (Reapproved 1977) Wall sampling in slurry systems, Nasr-el-din, N., Shook, C.A., Esmail, M.N., The Canadian journal of Chemical Engineering, Vol63, Oct 85 lsokinetic probe sampling from slurry pipelines. Nasr-el-din, N., Shook, C.A., Esmail, M.N., The Canadian journal of Chemical Engineering. Vol62. Apr 84 lsokinetic sampling at Expro, Personal communication from Booth, S., Jun 93 Guidelines for manual; sampling and analysis of hydrocarbon fluids, Steenson, B.E., EP 92-0980 Petroleurn products Liquid hydrocarbons Manual sampling, IS0 3170, First edition, 1975-07-01 Petroleum products Liquid hydrocarbons Automatic pipeline sampling. IS0 3171, First edition, 1975-12-01 Diagram from North Cormorant trials (2.05.2.h) indicating set-up of isokinetic sample quill through 2' ball valve. Turbulent pipe flow of dilute liquid-liquid dispersions: Drop sizes and criteria for homogenous BS&W distribution, Technical Progress Report WRC 197-76, Shell Development Co., A.. Karabelas, Dec 76, EP 04-8081
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Standard practice for Preservation of Waterborne Oil Samples, ASTM D 3325-90 Standard Practice for Preparation of Sample Containers and for Preservation of Organic Constituents, ASTM D 3694-92

Interesting report discussing the flow velocities required to obtain a representative sample of BS&W in oil. Shows that a given velocity must be maintained to ensure the droplets are fully dispersed. Even suggests sampling at 20% below the pipe centre line in some cases. ASTM Standard ASTM Standard, gives detailed procedures on the cleaning of both glass and HDPE sample bottles

Ref.1.07.2.a Ref.l.07.2.b

SlPM DridiiiK Mo~irirtl, EP 93-1315, Rev 1.1. N i w 1993, File numr = 99ZZBIB.DOC

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Bibliography
Standard Practice for Estimation of Holding Time for Water Samples Containing Organic Constituents, ASTM D 4515-85, (Reapproved 1990) Emulsions, Fundamentals and applications in the petroleum industry, edited by Laurier L. Schramm, SlPM Library VH 92-1, 1991, ISBN 0-8412-2006-9 Emulsions: Theory and practice, Paul Becher, 2nd Ed, SlPM Library HI 65-2,1965 Encyclopaedia of emulsion technology, edited by Paul Becher, Vols 1 to 3, SlPM Libraw HI EET-1 to EET-3,. 1983, ISBN 08247-1876-3 van Beest, W.J., Jan 1969, KSEPL RKGR.0006.69, EP 04-0068 General review of Shell's plants and facilities for production water treatment, van der Velden, J., Sept 1986 Theory of separation, Excerpt from Alfa Lava1 laboratoly separation LAPX 202 users guide. Designing oil and gas production systems: How to size and select water treating Arnold, K, Stewart Jr, M. World - equipment. . . Oil, March 85 Designing oil and gas production systems: Selecting a waste water treating system, Arnold, K, Siewart Jr, M. World Oil, May 85 Desiqn conceot for offshore Droduced water treatinq and disposal systems, Arnold, K.; Journal of Petroleumkechnology, Feb 83 Response of an oil/water containing vessel to imposed motion. Theoretical and experimental modelling, Waldie, B., White, G.trans IChemE, Vol70, Part A, Jan 92 Water treatment in oil fields. Not referenced Production water treatment Current and emerging technologies, E & P Forum report no 2.51/176, Nov 91 Treatment of produced water State of the art, E & P Forum, Technical review No 3, Oct 82 Oil/water separation by induced air flotation, Sylvester, N.D., Byeseda, J.J., Society of Petroleum Engineers Journal, Dec 1980 Also reprinted as SPE 7886, Society of Petroleum Enqineers. Wemco Depurator system, Basset, M.G., Society of Petroleum Engineers, SPE 3349, June 1971 Extract from "Design guidelines for oil water systems", Expro EN/039, Oct 85 The effect of air distribution on the induced air flotation of fine oil in water emulsions, Van Ham, N.J.M., Behie, L.A., Svrcek,W.Y., The Canadian journal of chemical engineering, V61, Aug 1983 The removal of emulsified oil particles from water by flotation, Angelidou, C., Keskavan, E., Richardson, M.J., Jameson, G.J., Ind. Eng. Chem., Process Des. Dev., voI16, no 4, 1977 Gas flotation of produced water, Strickland. W.T., Technical progress report WRC-EP 26-75-P, Shell Oil, EP 04-7155 ASTM Standard, gives methods to determine how long a sample may be stored without significantly affecting the accuracy of the subsequent analysis. Good recent textbook discussing most aspects of emulsions in the petroleum industry Classic emulsion reference, however relatively old Detailed discussions of all aspects of emulsion technology. Ref.l.07.2.c Ref.l.OB.1.a Ref.l.08.l.b Ref.l.08.l.c

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droplet size generated by a given mixing energy and the determination of optimum mixinq energy for coalescence. Mini version of the existing deoiling manual Discusses the theory regarding sedimentation and centrifugal processes. Discusses basic separation equipment and theory including skimmers, plate packs, skim piles, flotation Ref.2..01.2.b Ref.2.01.1 .a Ref.2.01 .l.b

I 1 Discusses SP Pack and gives an example of a selection

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lprocess for a waste water system. Does not consider droplet lsizes IPresents background theory behind oily water treatment including dropkt sizes, coalescence, flotation, Stokes law equipment etc. Investigates motion of oil and water in a tank and the effect of baffles

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IRef.2.Ol.l.c

IRef.2.01.1 .d
Ref.2.01.1 .e

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IGeneral discussion on deoilinq issues, includes water treating
requirements for effluent water treatment, injection water, enhanced oil recovery schemes. Discusses the recent performance of flotation, hydrocyclones, media filters and membranes. Discusses the operating performance of a range of traditional deoiling equipment Discusses effect of oil droplets sizes, gas bubble sizes on removal efficiency

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Ref.2.02.1 .a

,Discusses the original design and evolution of the Wemco. ]Very old reference. /Covers the Expro design guidelines for flotation units, including typical control schemes. Laboratory study investigating effect of bubble size and distribution, oil drop size and oil concentration. Discusses effect of salt water and surfactants on the flotation process. Excellent report investigating the variables affecting gas flotation. Investigates many variables including salinity, bubble size, chemicals and conducts field trials on both DGF and IGF units, Also finds gas sparging to be more efficient than a Jwemco. Discusses the Serck Baker flotation package with floating skimmers and pressure vessel design. Also mentions hybrid flotation system as desiqned for Beatrice. Modified a hydraulically induced flotation cell to dissolved gas tlotation using water from 1st stage separator as a gas saturated stream. Got significant improvement in flotation. Ordered from library, not yet reviewed

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Ref.2.02.1 .b

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IRef.2.02.1 .c
Ref.2.02.l.d Ref.2.02.1 .e

Advances in flotation unit design for produced water treatment, A.L. Casaday, Prepared for SPE Production Operations Symposium, Mar 21-23, 1993, SPE 25472, Mar 93 Operation and design of a hybrid flotation System, D.B. Rochford, Offshore technology conference, May 5-8,1986, paper 5247

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IRef.2.02.1 .g Ref.2.02.1 .h Ref.2.02.1 .i Ref.2.02.2.a

Operating experience with the Wemco depurator for effluent water treatment in the EBP field, Marriott, K.A., 3rdmeeting on water treating and pollution abatement techniques in refineries. Paper W-6-3, 1984 Induced static gas flotation, Midway Sunset field, Pilot testing and implementation, Barnes, M.C., Carpenter, M.A., Hluza, W.L., Production Division, Oct 11, 1990 Labuan Crude Oil Terminal. Chemlink induced air flotation field test, Nov 1990, (Draft) Labuan Crude Oil Terminal, L'eau Claire induced gas floatation field test, 29th May 7th June 1991, Shah, M., EP 91-1789 Black Bayou water treating facilities, H.W. Anderson, Shell Western E & P Onshore east division, Prepared for the 1984 FacKhem. Engineering conference, Paper WAlll4, May 1984 Operating experiences with depurator units (Make: Wemco) in the Auk field, Shell Expro, EP 05-9675, Jan 83 Wemco induced gas flotation product brochures

W.T. Strickland, SPE Journal, June 1980

Laboratory results of cleaning produced water by gas flotation,

Excellent article discussing several installations of Wemco flotation units and the operating experiences, including control schemes. Excellent discussion of a trial of the L'eau Claire Static Induced Gas Flotation system. Discusses modifications to the COntrOlS IDraft reoort of LCOT tests of Chemlink. Results very . .poor, efficiency only 15-20% Compares the Performance of a L'eau Claire and a Wemco. Better performance was obtained from the Wemco. Results for trials comparing Quadricell and Hydrocell IGF units. Hydrocell better performer and chosen for installation Covers operating experiences with Wemco type 84 in Auk field. Contains brochures, experience lists and some size and weight information for the Wemco flotation units. Contains brochures discussing the Monosep range of static induced flotation equipment, including four cell, two cell and one cell desiqns.

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IRef.2.02.2.c
Ref.2.02.2.d Ref. 2.02.2.e Ref.2.02.3.a Ret2.02.4.1 Ret2.02.4.2

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Monosep Veirsep flotation units, Brochures

Bibliography
L'eau Claire aas flotation, Brochures Ekof flotation (KHD Humboldt Wedaq) Serck Baker Gas flotation brochure

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Manual on the Shell parallel plate interceptor, Bataafse lnternationale Petroleum Maatschappii, MFD Oil-water separator process design, Chapter 5, Manual on disposal of refinery wastes, Volume on liquid wastes, API, 1st Ed, 1969, Constructiondetails of gravity-type separators, Chapter 6, Manual on disposal of refinery wastes, Volume on liquid wastes, API, 1st Ed, 1969, Rotating oil drum skimmer, Elf Antar France Extract from "Design guidelines for oil water systems", Expro EN/039, Oct 85 Separator internals for liquid-liquid or liquid-solid separation Pielkenrood systems, Teeuwen, A,, Oct 1992 Only gravity to purify produced water, Reigersman, A,, Pielkenrood, Petrochem Nr 8 (1990) Deoiling industrial waste water. Design and operation of the "CPI" (Corrugated Plate Interceptor), Report MF 81-0700, May 1981 Drainage and primary treatment facilities, Shell DEP 34.14.20.31-Gen, Oct 1992 (Draft) Evaluation of a skim tank or CPI separator alternative for effluent circa 1983 Prediction of the performance of plate pack separators Implications to design, Davies, G., Not referenced

Brochures, diagrams, proposal for unit Brochures and results from a Berlin pilot plant Informationon Serck Baker flotation, both mechanical and hydraulically induced. Also see Serck Baker equipment manual reference 9.02. Extracts from manual for the fitting of PPI plates to an API separator. Contact MFEC/24 for the oriqinal copy Discusses the application of Stokes law to sizing of API separators Discusses construction details of API separators Brochure for a oleophilic rotating drum skimmer available from Elf Antar Covers the Expro design guidelines for plate pack systems. Methods for the preliminary sizing of plate packs, written by Pielkenrood. Discusses the preference for flat plates over corrugated plates in the cross flow design Discusses the sizing, construction and operation of the Shell standard CPI Draft of updated DEP. Not yet issued. Discusses CPI installations. Gives size and cost information for evaluating skim tank and Detailed discussion predicting the outlet concentration from plate packs by considering the separation of the droplet size distribution. Discusses the sizing of plate pack on the basis of studying the droplet size distributions and predicting the actual outlet concentration for a given inlet distribution. Detailed paper discussing mechanisms of droplet coalescence on inclined plate surfaces. Note confirming MF divisions recommendations the Re is 800 for flat plates and 400 for corrugated. Short test of Fram CPI. Results good, however droplet size not known. Taken from Appendix B of report Ref 2.09.2.C Discussion on the treating of ballast water using a plate pack CPI system. Covers the various types of plate packs Covers the various types of plate packs Brochures and experience listing Plate pack coalescers and separators. Uses a unique hexagonal structure Excellent article discussing the installation and performance of hydrocyclones on the Murchison and Hutton platforms. General article describing hydrocyclones. Discusses droplet size distributions, compares with flotation. Vortoil information describing new developments including Ihe K liners, different applications (e.g. pre separation, oil dehydration and a control scheme for a centrifugal pump cyclone system Discusses the performance of progressive cavity pumps in a hydrocyclone system, control scheme given with level control valve on effluent line and pressure control on recycle. General article on Murchison/Hutton installations. Summary of some of the first hydrocyclone installations by BWN Vortoil in Australia. Discussed general principles,

Ref.2.02.4.3 Ref.2.02.4.4 Ref.2.02.4.5

Ref.2.03.1 .a
Ref.2.03.1 .b Ref.2.03.1 .c Ref.2.03.1 .d Ref.2.04.l.a Ref.2.04.l.b Ref.2.04.l.c Ref.2.04.1 .d Ref.2.04.1 .e Ref.2.04.1 .f %k04.1

-

.g

The design of plate separators for the separation of oil-water dispersions, Rowley, M.E.. Davies, G.A., Chem Eng Res Des, Vol. 66, July 1988 Plate separators for dispersed liquid-liquid systems: Hydrodynamic coalescence model, W. Meon, W. Rommel, E. Blass, Chemical Engineering Science, Vol48, No.1 , pp 159168,1993 Note from A. Bos, MFTB/201 Test with Fram CPI, Schoonebeek, The Netherlands, 1981. Appendix B of report Ref 2.09.2.c Tanker ballast water treating plant meets tough specs, Oil & Gas Journal, Dec 4. 1978 Skimovex brochure Nijhuis brochure RossmarWPielkenrood plate pack brochures Wemco Pacesetter plate pack Hydrocyclones: A solution to produced water treatment, Meldrum, N, Conoco, Presentedaf OTC 1987,OTC 5594. Produced water treatment with Vortoil hydrocyclones in high pressure gas production, Wolfenberger, E, (Conoco), Presented to the Houston chapter of the American filtration society, Jan 1992. Advancements in liquid hydrocyclone technology, Wafer management offshore conference, Oct 1991, Vortoil Use Of low shear pumps in conjunction with hydrocyclones for improved performance in the clean-up of low pressure produced water. Flanigan, D, (Conoco), Presentedat SPE 7989,SPE 19743, Oct 1989 Conoco's water treatment upgraded with hydrocyclones, Rosie, K, Conoco, Ocean Industry, Dec 1991/Jan 1992 Hydrocyclonesfor treating oily water: Development and field testing in Bass Strait, Presentedat OTC 7985, OTC 5079

Ref.2.04.1 .h Ref.2.04.l.i

Ref.2.04.l.j Ref.2.04.2.a Ref.2.04.3.a Ref.2.04.4.1 Ref.2.04.4.2 Ref.2.04.4.3 Ref.2.04.4.4 Ref.2.05.1 .a Ref.2.05.1 .b

Ref.2.05.1 .c

Ref.2.05.1 .d

?ef.2.05.1 .e 7ef.2.05.1 .f

Pqqe Bibliojiruphy-6

SlPM Droiliiig

Miiiiiiiil.

EP 93-131.5. Rev I . I * Nriv 1993, File niime = YYZZBIB.DOC

Bibliography
Collection of papers from 1980 htemational Conference on Hydrocyclones, Includes the following: 1. Determination and use of residence time distributions for two hydrocyclones, Thew, M.T., Silk, S.A., Colman, D.A. 2. Small-scale experiments on hydrocyclones for de-watering light oils. Colman, D.A., Thew, M.T., Comey, D.R. 3. Hydrocyclonesfor oil/water separation, Colman, D.A., Thew, M.T., Comey, D.R. 4. Correlation of separation results from light dispersion hydrocyclones, Colman, D.A., Thew, M.T. 5. RTD characteristics of hydrocyclones for the separation of light dispersions, Thew, M.T., Wright, C.M., Colman, D.A. 6. The effect of split ratio on heavy dispersion liquid-liquid separation in hydrocyclones, Smyth, I.C., Thew, M.T., Colman, D.A. 7. Hydrocyclone for the treatment of oil-spill emulsions, Robertson, D.S., Oswald, B.J., Colman, D.A., Thew, M.T. 8. The concept of hydrocyclones for separating light dispersions and a comparison of field data with laboratory work, Colman, D.A., Thew, M.T., Lloyd, D.D. Deoiling hydrocyclones: Separation of Forties dispersions at temperatures up to 9O"C, Nezhati, K., Thew, M., EP 90-3291, July 1988 Reduction of residual oil content in produced water at offshore gas production platform P/6A, Noort F.J. op ten, Etten, J.P., Donders, R.S., SPE 20882, Oct 1990 Low pressure hydrocyclone separator, Flanigan et al., US patent number 4,844,817, Jul4, 1989. Conoco fax, detailing claimed hydrocyclone performance for a selection o f installations Expro experience with hydrocyclones. Record of meeting with S.R. Moore of Expro, 1/2/91 Water in oil separation and produced water treatment report, Troll Olje, April 1992 Experience with Vortoils in the Murchison field, Choufoer, Norske Shell, Aug 1986 LCOT Hydrocyclone pilot tests, Mar 1980 Contains some of the foundation articles discussing the principles of hydrocyclone performance. Reference 4 in particular is the basis for the correlations presented in Appendix I. Ref.2.05.1 .g EPLIB No CD.200.033

Discusses the performance of the cyclone at a range of temperatures and droplet sizes. Discusses trials of a centrifuge, hydrocyclone and membranes for offshore gas platform. Patent application by Vortoil on the use of pumps to feed hydrocyclone systems. Discusses trials to determine the shear characteristics of different pumps and the criteria required to Qet low shear from a centrifuQe pump. Includes two cases illustrating the effect of downstream degassing vessel in reducing eflluent hydrocarbon content Discusses the Expro experience with hydrocyclones, particularly effects of sand and the use of the degassing vessel to further reduce the oil content. Discusses the proposed water treatments system for Troll Oil field, compares cyclones and centrifuges, investigates use of Chitosan for coalescence. Discusses the Murchison installation and performance. Comments on increasing the reject ratio to 30% to deal with oil contents in the order of 8%. Discusses hydrocyclone tests at Labuan, results were satisfactory, though not as high as normally expected from hydrocyclones. Use of chemicals has been proposed to improve performance. Also has graph noting a relationship between hydrocyclone outlet concentration and improvement by degassing vessel. This was roughly linear with a 10 15% reduction in effluent concentration. Results of field trials. Results favourable. Considers droplet size analysis Conoco report. Compares the performance of F and K liner Vortoils. Significant improvement with K liners. Also notes effect of corrosion inhibitor. Discusses the application of the KSLA photomicrograph technique to the hydrocyclone trials. Contains background information of droplet size distribution, grade efficiencies, cutoff diameters etc. Discusses the application of the KSLA photomicrograph technique for investigating the performance of the hydrocyclone. Discusses the use of several correlations for predicting the performance of the hydrocyclone lor different droplet size distributions. Compares the performance of hydrocyclones and centrifuges. Discusses the effect that sand has had on the Shell Expro installations. Briefly discusses the operating problems experienced with hydrocyclones to date. A collection of information describing the design, installation and commissioningof the Kittiwake pumped hydrocyclone system. Vortoil proposal for the Maui A water treatment system. Gives some interesting information such as amount of gas allowed in feed to K liners, use of strainers, reject port backflushing and limit of 30 bar pressure differential to minimise sand erosion Gives normal information expected in a specification such as scope of supply, codes and standards, inspection testinq etc. Operation guide for hydrocyclones.

Ref.2.05.l.h Ref.2.05.1 .i

Ref.2.05.2.a Ref.2.05.2.b Ref.2.05.2.c Ref.2.05.2.d Ref.2.05.2.e

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Hydrocyclone field trials in Marmul, Rima and Lekhwair stations, PDO, Jan 1991 Sluis, 0. Vortoil hydrocyclone trial for Golar Nor offshore and Norske Hydro on Petrojarl 1 production ship, Troll west gas province, April 1991 North Cormorant hydrocyclone trials, Zeef, E., Visser. H.P., Nov 1987, EMTR.88.002, EP 88-2613 The performance of the Vortoil hydrocyclone for separating dispersed oil from water. An analysis of the North Cormorant Trials, Weve, D.N.M.M, Paardekooper, St., AMTR.87.004, EP 87-0572 Maui A Produced Water System, Position Paper, July 1992 Sand production, erosion and hydrocyclones, Communication to Shell Todd Oil NZ, 13/5/92 Status of Expro hydrocyclone systems, Record of telephone conversation, 10/1/91 Kittiwake produced water system. Proposed Maui produced water treatment system.

Ref.2.05.2.f Ref.2.05.2.g

Ref.2.05.2.h

Ref.2.05.2.i

'lef.2.05.2.j 'lef.2.05.2.k 'lef.2.05.2.1 ?ef.2.05.3.a W.2.05.3.b

Hydrocyclone specifications. Example from Vortoil of a specification for the purchase of a hydrocyclone package North cormorant hydrocyclone skid operating and troubleshooting guide, Moore, S.R., April 1990, Shell Expro Draugen hydrocyclone data sheet and package specification, Oct 1989 General arrangement diagrams for Eider Alpha hydrocyclone package, 1992 Vortoil Separation Systems, Brochure

Ref.2.05.3.c Ret2.05.3.d Ref.2.05.3.e Ref.2.05.3.f Ref.2.05.4.1

Detailed data sheet and specification for the Draugen hydrocyclone package. Shows arrangement of hydrocyclone package A series of 7 product bulletins which give informalion on process design, control schemes and the size and weights of G and K liner packages. Also brochure from Mape, a French manufacturer of Vortoil systems.

Merpro Montassa Ltd, Brochure and information package Natco/Krebs Hydrocyclone Brochure Serck Baker hydrocyclone brochures MPE Hydroswirl hydrocyclones Design of a High-Rate, High-volume OiliWater Separator, Stires, J., Journal of Petroleum Technology, November 1982, pp 26372644 Design concepts for offshore produced water treating and disposal systems, Amold, K.E., Journal of Petroleum Technology, February 1983, pp 276-283 Evaluation of a skim tank or CPI separator alternative for effluent water treatment in the Sayala filed development, PDO Oman, circa 1983 Residence time distribution in gravity oil-water separations, Zemel, E., Bowmans, R.W., Society of Mechanical Engineers, Paper SPE 6527, Journal of Petroleum Tech, Feb 78, pp275-282 Efficient separators show good hydraulic behaviour, Bernie Zemel, Shell Development Co., Oil & Gas Journal, Dec 26,1977 Rapid filtration, Ives, K.J., Water Research, 1970, V01.4, pp201223 Art, science and filter media 2,Purchas, D.B., Filtrafion & Separation, July/Aug 1980 Filtration through deep beds, Treanor, A.I., Process Biochemistry, Sept 1971 Review of the oerformance of the Hvdromation crushed walnut filter tests in Mina al Fahal, Marmu1,'Suwaihat and Qarn Alam, Dec 1991 -July 1992, Davite, G., PDO Report BDD/159/92 Comoarison of 2 filtem.. Hvdromation and Dvnasand. Auo 1985 ,

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Gives information on control system, turndown, backwashing and the setting of the reject ratio to remove massive oil contents. Brochures etc. Information on the Oilspin II hydrocyclone. Note that new hydrocyclone design expected late 1993. Also see Serck Baker equipment manual Ref.9.02 Brochures. Also see full equipment manual Ref.9.03 Design of a skim tank derived from API design principles. Also investigates the residence time distribution of flow through the vessel. Selection of articles which discuss the recommended residence time for a large volume skim tank Gives size and cost information in evaluating skim tank and Shell CPI. Discusses the residence time inside separation vessels. Found poor distribution and significant short circuiting Good article illustrating the poor residence time distributions in skim tanks and other vessels including baffled designs. Discusses general theory of deep bed filtration Discusses the characterisation methods for various types of filter media Discusses general theory of deep bed filtration Good trial of the Hvdromation filter Surnrnaw 01 Schoonebeek Hvdromation results with Fredericia Dynasaid results. Contains references to original reports As described, date not known Hydromation report into test results for treatment Of produced water in Wyoming Hydromation report into test results lor treatment of produced water Hydromation report into test results for treatment of produced water German report of BEB Hydromation tests Includes raw results Raw results from trials only Raw results from trials Only Results of InPlant trial. Generally good results with oil, though as good Discusses the range of filters used by Shell Canada and the actual installations including media filters and pre-coat filters. Quotation for Hydromation package Results of Nigerian installation Process design study examining the requirements for filtration and injection of both produced water and sea water. Extracts 01 reports only. Pretreatment stage upstream of evaporation plant WalnuVpecan shell filter Walnut shell lilter, includes informalion on use of test units. Dual media filters, also includes information on trial units Brochure Brochures and background on InPlant filters Communication from Shell Canada Not referenced Alfa Laval guide to the theory behind disk stack centrifuges. Discusses theory behind waste oil recovery, including solids removal, emulsions and the centrifuges that may be used etc. Discusses trials of centrifuge. hydrocyclones and membranes for offshore gas platform. Discusses the proposed water treatments system for Troll Oil field, compares cyclones and centrifuges, investigates use of Chitosan for coalescence. Compares the performance of hydrocyclones and centrifuges. Trial of a continuous discharging centrifuge system on some of the worst effluent streams. Results were considered good.

Ref.2.05.4.2 Ref.2.05.4.3 Ref.2.05.4.4 Ref.2.05.4.5 Ref.2.06.1 .a Ref.2.06.l.b Ref.2.06.l.c 'Ref.2.06.l.d Ref.2.06.1 .e Ref.2.07.1 .a Ref.2.07.1 .b Ref.2.07.1 .c Ref.2.07.2.a Ref.2.07.2.b Ref.2.07.2.c Ref.2.07.2.d Ref.2.07.2.e Ref.2.07.2.f Ref.2.07.2.g Ref.2.07.2.h Ref.2.07.2.i Ref.2.07.2.j Ref.2.07.2.k Ref.2.07.3.a Ref.2.07.3.b Ref.2.07.3.c Ref.2.07.3.d Ref.2.07.3.e Ref.2.07.4.1 Ref.2.07.4.2 Ref.2.07.4.3 Ref.2.07.4.4 Ref.2.07.4.5 Ref.2.07.5.a Ref.2.07.5.b Ref.2.08.1 .a Ref.2.08.1 .b Ref.2.08.1 .c Ref.2.08.2.a Ref.2.08.2.b Ref.2.08.2.c

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Hydromation Deep bed filter test, North sea water filtration, Norwegian under water institute, Bergen, Norway Test results of oil and suspended solids removal from produced water in heavy crude oil production, Kozar, D, March 1980 Hydromation company deep bed filtration test. Union Oil, Grayling (Beaver creek), Michigan, 1980 Hydromation report from Shell Espana Castellon field, tanker vessel Delta Erprobung der 'Deep bed filtration" system Hydromation auf dem Betriebsqelsnde der BEB im Ruhlermoor, May 1983 Field trials with a Hydromation filter lor production water treatment, Schoonebeek oil field, Sept 84, Nam report EM/1176 Hydromation, raw results from Flotta sea water filtration trials. May 1984 Hydromation, raw results from BEB Ruhlermoor filtration trials, Jan 1984 InPlant Unit. Field trials with a Separator Filter Coalescer in Mina BDD/150/92 Filter data survey. Labuhn. I., Shell Canada, Aug 1978, EP-no. 51344 Hydromation, Quotation package for a 10,000 bpd produced water clean-up package, June 1983 Hydromation, results of Elf Aquitaine Nigeria Water injection process design study, Oil Plus Reports 4239REP-08 and 4239-REP-10, For Shell Expro PFD for Schoonebeek Hydromation deoiling filter Wemco Silver Band Brochures Hydromation brochures Serck Baker Kalsep spiral cord filters InPlant filters Summary of Shell Canada experience with a range of filters, May 90 Summary of available filtration information on Hydromation and Silver band filters. Not referenced. Theory of disk stack centrifuges lor the oil field industry, Alfa Laval product information, 1989 Waste oil recovery, Alfa Laval product information

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Reduction of residual oil content in produced water at offshore gas production platlorm P/6A, Noort F.J. op ten, Etten, J.P., Donders, R.S., SPE 20882, Oct 1990 Water in oil separation and produced water treatment report, Troll Olje, April 1992 Maui A Produced Water System, Position Paper, Report92/029, July 1992 Labuan crude oil terminal, Alfa Laval disc stack centrifuges field test, Sept-Dec 1991, Shah, M

Pugc Biblicigrupli)4

SIPM Droiling Marirrrrl. EP 93-1315, Nrv 1.1, Nov 1993. File nume = 99ZZBIR.DOC

Bibliography
Centrifuge pilot test at MPNl's P/6-A platform, Donders, R.S., Perk, O.v.d., Mobil Producing Netherlands, April 1990 Produced water disposal trials by M w s k Olie og Gas, GrossPetersen, J., Jsrgensen, J. Sept 1991 Centrifuge trials on terminal emulsion and effluent water, Abraham, G., Seria, Brunei, Dec 1989 Discusses trial of centrifuge on Mobil platform. Excellent results obtained in trial Discusses results of both membrane and centrifuge trials Found the centrifuge to be successful for treatment of residual emulsions and effluent water treatment. However existing heater treaters were considered more economical to operate for emulsions and centrifuges would be too expensive for the large effluent water flow rates. Quote for centrifuges. Quote for centrifuges. Specification for disc type centrifuges, including discussions on control and interface position etc. General brochures on Alfa Lava1 centrifuges. Includes details on a centrifuge packaged into a container module. Brochures on the Leo system only Covers conventional and decantinq type centrifuges Centrifuges Discusses dissolved air and solids separation, however many of the findings and equations are relevant to deoiling. Brief background on Henry's law Use of flotation/plate pack system for a Dutch refinery Good summary of the Pielkenrood DGF units, with some sizing information and general theory. Well written and still relevant information Investigates the effect of bubble size and concentration and the coagulation/flocculationstages of DGF. Concludes chemical pre treatment is the most important step. Field trials in Brunei on hydrocarbons and solids removal Field trial of DGF in Brunei Field trial of flotation/plate pack system for produced water at Schoonebeek, The Netherlands Investigation into the poor performance of a DGF. Found fluctuating feed conditions, non-optimised use of chemicals. Investigated use of centrifuge and solvent extraction to improve performance. Brochure with size and weiqht information Brochure with size and weiqht information Brochure with size and weiqht information Brochure with size and weight information Ref.2.08.2.d Ref.2.08.2.e Ref.2.08.2.f

Budget quote for OFPX517 centrifuges, Oct 1991. Budget quote for Leo centrifuges, Oct 1991. High speed disc stack three phase centrifuges, Type OFPX-413, container modules, Alfa-Lava1 Alfa-Lava1general brochures Alfa-Lava1 Leo brochures Pieralisi brochures Westfalia brochures Dissolved air flotation for water and waste water treatment, Ward, AS., Trans IChemE, Vol70, Part B. Nov 1992 Extracts on Henry's law from Chemical Engineering Handbook, 6th ed, Perry, pp 4-60,61, 14-9, 14-15 Floc/float system cleans desalter effluent, Kleen, H., Marson, H.W., Oil& Gas Journal, Sept 8, 1980 Treatment of produced water from oil and gas production platforms by dissolved gas flotation (DGF), Reigersman, A. R O Conference, Offshore technology & environmental control on the Dutch shelf, Feb 16, 1990 Filtration, flocculation and flotation, Chapter 9, Manual on disposal of refinery wastes, Volume on liquid wastes, API, 1st Ed, 1969, A conceptual model for dissolved air flotation in water treatment, Edzwald, J.K., Malley Jr, J.P., Yu, C., Water supply, Vol9, Jonkaring, pp141-150, 1991 Evaluation of induced gas and dissolved air flotation units for water treatment, Kwant, J.W.H., Informal contribution to the production technology conference, Nov 1982 Dehydration water treatment with dissolved air flotation, Nuis, D.A.E., Kwant, J.W.H, Dec 1982, Brunei. EP-no. 57250 Dissolved gas flotation, Water treatment field test on Schoonebeek produced water, Leerlooijer, K, Dec 1981, EP-no. 55594, NAM Effluentwater quality trial on AWG-1, SPC/22 Jan 1987, NAM, Report 183/86 Serck Baker DAF brochure Nijhuid Water brochure Skimovex flotation brochures RossmarWPielkenrood flotation brochures May 1993 Gas condensate water treatment using rotary hydrocyclone, Triponey, G., Woillez, J. Rotary cyclone will improve oily water treatment and reduce space requiremenVweight on offshore platforms, Gay, J.C., Triponey, G. Bezard, C., Schummer, P., Society oiPetroleum €ngineers, SPE16571, Sept 1987 Dynaclean: A step fofward in produced water treatment, Bezard, C. General technical soecification. . Dvnaclean , Personal communication from Dynaclean discussing design conditions, intermittent flow configuration and effect of solids on the rotaty cyclone. A field comparison of static and dynamic hydrocyclones, Jones, P.S., SPE 20701, 1990 Dvnaclean brochures. Fax from Dynaclean listina trials and installations of the rotaw cyclone. The Serck Baker tubular precoat filter, Laboratory scale test work on bipolvmer solution Precoat filtration trials with a Serck Baker Dlant on Dunlin A, Pelgrom, J.J., Jan 1981, Shell Expro Celite Filter Aids D N Brochures

Ret.2.08.3.a Ref.2.08.3.b Ref.2.08.3.c Ref.2.08.4.1 Ref.2.08.4.2 Ref.2.08.4.3

Ref.2.09.1 .c

1 Ref.2.09.1 .d

Ref.2.09.1 .e Ref.2.09.1 .f Ref.2.09.2.a Ref.2.09.2.b Ref.2.09.2.c Ref.2.09.2.d

Ref.2.09.4.1 Ref.2.09.4.2 Ref.2.09.4.3 Ref.2.09.4.4

Summary of the principles behind the rotary hydrocyclone and summarises the results of the OWTC trials Discusses limits of static hydrocyclones and benefits of dynamic hydrocyclones. Includes results of test work conducted on two platforms. Gives some comparison of size and weight of units Paper from Serck Baker discussing design and sizing of Idynamic hydrocyclones 1 Information oack containina auide to the selection and specification' of a Dynacle&&clone. Very useful Fax from Serck Baker Good comparison between dynamic and 2 static cyclones. Concludes that the rotary hydrocyclone has the advantages of separating a smaller droplet size with a lower pressure drop. Dynaclean brochure with size and weiqht information. Fax from Serck Baker Test work carried out for diatomaceous earth type filter on bipolymer solution Trials with Drecoat filter. Only partially successful . . Discusses the backqround to diatomaceous earth filter media Cloth type filter, does not appear to be used in oil industry, can be used with pre-coat Tube filter suitable for pre-coat filter operations Brochure Cleanable cartridqe designed to replace disposable cartridges Etched disc cartridge type filters provide robust construction Iand absolute ratings from 3 to 40 microns (Full range of cartridge type filters, see full catalogue Ref.9.01

Ref.2.11 .I .a Ref.2.11.1 .b

IRef.2.ll.l.d Ref.2.ll.l.e Ref.2.11.1.f Ref.2.11.4.1 Ref.2.11.4.1 Ref.2.12.2.a Ref.2.12.2.b Ref.2.12.4.1 Ref.2.12.4.2 Ref.2.12.4.3 Ref.2.13.4.1 Ref.2.13.4.2 Ref.2.13.4.3

I

Ref.2.1l.l.c

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Serck Baker tube filters, Brochure 3M Filter bags Serck Baker stainless steel cartridges Vacco metal etched disk filters Peco

I I

IRef.2.13.4.4

I I I

SlPM Deoilina Mrrrr~rol,EP 93-1315, Rrv 1.1, Niiv 199.1, File iioiiie = 99ZZRIB.DOC

Puge Biblirigruphy-9

Bibliography
Serck Baker The treatment of oily water by coalescence: Techniques and applications developed by Elf-Aquitaine, Secq, A,, Seureau, J. The treatment 01 oily water by coalescing, A. Bevis, Filtration 8 Separation, July/August 1992 Condensate cleans up oily produced water, C. Dean Cockshutt, G. Fode, Oil 8 Gas Journal, Nov 25. 1991 lnfilco Degremont, Report from trials of Colexer pilot study trials, Field 32, Lost Hills, California The SP Pack lree flow coalescer, Barnes, M.C., Shell Western E & P, Oct 1990 Coalescer evaluation for the Goodwyn A platform, Smith, P.G., Mar 89, CSIROMoodside, EP no.89-1365 Improving coalescer performance, Smith, P.G., Swift, J.D., Nov 1988, CSIROANoodside, EP no. 89-1366 Use of a mesh interceptor for water clarification, W.D. Grimes, Shell Offshore Inc, Prepared for the 1988 FacilitiesKhemical engineerinq conference, Paper TMI 2, March 1988 Skimovex lnverto coalescers Plenty Metro1general brochure Degremont (address only) Natco VFX (upflow filter/coalescer brochure) and Performax coalescer Elf Anvar brochures Monosep Spiralsep Peco Knitmesh MPE SP Pack Membrane svstems for oilv water treatment. Paoer No. 3/06 PE. Buss, G., S 5 2 KSLA, Noi92, Prepared for'the'1992 Production and process technology conference, The Hague Testing and design of ceramic membrane filters for treating of produced water, Chou, C.C.. Grimes, W.D., Schmaltz, K.S., Shell Oil, Oct 1990, prepared for the 1990 Facilities/Chemical Engineering Conference. Presentation on membrane technology, Global Engineering Production water disposal, An evaluation of membrane technologies vs. conventional treating techniques, Jan 89 Dec 89, KSLA report for PDO Oman, Vasmel, H., Schuurmans, H.J.A. Reduction of residual oil content in produced water at offshore gas production platlorm P/6A, Noort F.J. op ten, Etlen, J.P., Donders, R.S., SPE 20882, Oct 1990 OiVwater separation by membrane systems, Buss, G.Y.. Vasmel, H, Schets, T.F.M, May 90, KSLA, prepared for the 1990 SlPM Production Technology Conference Membranes for water clean-up, Callaghan, D. Feature article lor Process Bulletin, May 1990 Range of cartridge type filters, see full catalogue Ref.9.02 Discussion of coalescing theory. Also includes relerences to the Elf Anvar process Excellent article by Alan Cobham Engineering discussing the design and process variables affecting cartridge type coalescers. Discusses the use of hydraulic coalescence to improve removal of heavy oil from water by recycling condensate to water stream. Results of filter/coalescer trials Results of installing an SP Pack into a skimming tank Investigation into 5 different coalescer elements for the removal of water from condensate. Investigation into improving the performance of the water in condensate coalescer on North Rankin, Australia Improved the performance of a plate pack interceptor by installing polypropylene mesh after the plate pack to capture and coalesce small droplets. Downflow deep bed filter/coalescer Includes some general references and a filtration experience list Address and PFD for a Degremont upflow filter/coalescer Brochure Brochures on upflow and downflow Elf Anvar coalescedfilters. Also includes several trial reports and reference lists Brochure Brochures, also see Peco equipment manual, Ref.9.01. Brochures and experience Brochures, also see MPE equipment manual, Ref.9.03 Revlew of all known work on membranes for oilv water cleanup conducted within Opcos and OWTC Discussion of the successful trials and design of a full scale Alcoa membrane system to be installed on a platform for Shell Oil. Compares some of the membrane rivals Presentation by Global Engineering on all types of membranes based on work conducted for the UK Dept of Enerqy Discusses the potential application of membrane technology to water clean up. Discusses concepts of pervaporation for removal of dissolved hydrocarbons. Discusses trials of centrifuge, hydrocyclones and membranes for offshore gas platform. Summarises the results of the OWTC Phase I membrane trials and the pervaporation concept being tested by KSLA Briefly discusses various tests conducted by Mobil and NAM for membranes and oily water. Also mentions sulphate reducing membranes. Discusses current state of application of membranes for oily water clean up. Lists potential suppliers of membranes. Discusses results of OWTC membrane trials and discusses the principles behind pervaporation. Discusses the use of membranes for clean up of dispersed and dissolved oil. Ref.2.13.4.5 Ref.2.14.1 .a Ref.2.14.1 .b Ref.2.14.1 .c Ref.2.14.2.a Ret2.14.2.b Ref.2.14.2.c Ref.2.14.2.d Ref.2.14.2.e Ref.2.14.4.1 Ref.2.14.4.2 Ref.2.14.4.3 Ref.2.14.4.4 Ref.2.14.4.5 Ref.2.14.4.6 Ref.2.14.4.7 Ref.2.14.4.8 Ref .2.14.4.9 Ref.2.15.l.a Ref.2.15.l.b

Ref.2.15.l.c Ref.2.15.1 .d

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Ref.2.15.1 .e Ref.2.15.1 .f Ref.2.15.1 .g Ref.2.15.l.h

Recent advances in the application of membrane technology for the removal of oil and suspended solids from produced waters, Zaidi, A., Simms, K., Kik, S. Nelson, R., International Produced Water Symposium Feb 4-7, 1992, San Diego OiVwater separation by membrane systems, Buss, G.Y.. Vasmel, H., Schets, T.F.M., ST/1, KSLA, 3 May 90, Prepared for 1990 SlPM Production Technology Conference, Paper 3P/05 Production water disposal, An evaluation of membrane technolooies vs. conventional treatina techniaues. . . Vasmel. H.. Schets, f.F.M., 1989, Draft Reverse osmosis and ultrafiltrationsolve seoaration Droblems. ' Gooding, C.H., Chemical Engineering, Jan 7 1985 Treatment and disposal of waste waters produced with coalbed methane by reverse osmosis, Simmons, B.F., Produced Water, Ray, J.P., Engelhart, F.R., Plenum Press, 1992, pg 593 Removal of oil, grease and suspended solids from produced water with ceramic crossflow microfiltration, Chen, A.S.C., Flynn, J.T., Cook, R.G.. Casadav. A.L., SPE Production Engineerina,
I .

Ref.2.15.1 .i Ref.2.15.l.j

I Discusses RO and ultrafiltrationand qeneral membrane

considerations. Indirectly useful Discusses the application of reverse osmosis for oily water cleanup. Claims in some cases technique can be technically and economically feasible. Discussions 01 the olfshore trials of the Alcoa Petrolux system. Also see 2.15.1 .b

IRef.2.15.1 .k
Ref.2.15.1.l Ref.2.15.l.m

Oil and suspended solids removal from produced water using ultrafiltrationand microfiltration, Zaidi, S. Kok, K. Simms, J Schmidt, Wastewater Technology Centre. Burlington, Canada Preliminary ultrafiltrationexperiments on formation water from oil platforms, Idema, W., Stork membranes, Jan 89 Membraanfiltratieproevenop oliehoudend formatiewater, Nov 1990, NAM Report 18703, Dutch language (Results of Stork membrane trials at Schoonebeek) Produced water disposal trials by Marsk Olie og Gas, GrossPetersen, J., Jsrgensen, J. Sept 1991 Review of the execution of the membrane test carried out on K7FA-1 between 30/3/92 and 1/6/92, from SEFI15, NAM

Good article summarising the experience of a range of membrane trials in Canada and the US. Lists a range of membrane manufacturers. Investigates the suitability of Stork ultra filtration membranes applied at pilot plant level for filtration of oily water. Results of Stork membrane trials conducted at Schoonebeek to select the best membrane IOapply to produced water. Discusses results of both membrane and centrifuges trials Discusses the problems experienced in conducting an oflshore membrane trial utilisinq the Hoogovens membrane.

Ref.2.15.l.n Ref.2.15.2.a Ref.2.15.2.b Ref.2.15.2.c Ref.2.15.2.d

fuge Bib/iogrup/~y 10

SlPM Deoiling Mcinuul, EP 93-1315. Rev 1.1. Nov 1993. File nume = 99ZZBIB.DOC

Bibliography
Ultrafiltration field pilot testing for the treatment of produced water, (Zenon membranes) Volume I and 11, June 1990, EP 90-3729 The trial of an SDI membrane unit on Expro's lnde Julliet between 23 April and 22 June 1993, G. Buss (KSLA), B Touw (Expro, Lowestoft), G. van Hirtum (KSLA), Draft report Detailed report on field trials at the Shell Canada Peace River development for use of a Zenon ultrafiltration membrane for treatment of produced water from a steam stimulated heavy oil reservoir. Found gradual fouling by clays over time and could not establish a constant flux rate. Draft report of a trial of the SDI membrane with dispersed and dissolved hydrocarbons. Good results with dispersed hydrocarbons, but could not remove all dissolved

Stripping of dispersed hydrocarbons from water, Visser, R.M., van Huuksloot, A., Visser, H.P., EE.4 KSLA, 20 Sept 1991 (See Ref.3.02.2.b) Drying of natural gas condensates by stripping with dried gas, Part I, Sizing of the stripper column lor the NAM-F3 project, J.A.M. Spaninks, A.E. Cornelissen, KSLA AMER.82.052, EP 056091 Drying of natural gas condensates by stripping with dried gas, Part II, Model experiments, A.E. Cornelissen, H.P. Visser. KSLA AMER.83.037, EP 05-9146 Drying of natural gas condensate by stripping with dried gas, Part Ill.A tray-to-tray computer program lor stripper column design, A.E. Cornelissen, KSLA AMGR.83.211, EP-59207.

drocarbons could not be removed. Suoersedes reDort def.3.02.2.c Investigates stripping of dispersed hydrocarbons from water. Superseded by report Ref.3.02.2.b First report discussing the mass transfer mechanisms for a condensate stripper. Gives an example calculation for estimating the water removal rate at 50% and 90% removal of water. The theory and models proposed in Part I (EP 05-6091) are developed further and tested in laboratory trials. Measured stripping rate was found to be faster than predicted by model. Discusses the computer program COLUMN used to calculate stripping performance of a condensate dehydrator using dry gas stripping. Program allows user to determine required number of trays. Gives listing of program (Fortran) and discussion of theory behind program. Program based on results from Pari I (AMER.82.052) and Part 11 (AMER.83.037) Results of condensate stripping experiments conducted on the NAM-fb-1 platform using a packed column.

Ref.3.02.2.c Ref.3.02.2.d

Ref.3.02.2.e Ref.3.02.2.f

Drying of natural gas condensate by stripping with dried gas Field experiments on the NAM K-15-fb-1 platform, KSLA AMER.84.036

Ref.3.02.2.g

SIPM Denilinl: Maiiircrl. EP 9.3-1315, Rrv 1.I . Nov IY93. Filr

iwiiw

= 99ZZlllR.DOC

PuRe Biblio#ruphy-l I

Drying of natural gas condensate by stripping with dried gas Further field experiments on the NAM K-15-fb-1 platform, KSLA AMER.86.028 Bio-reclamation of oil field produced waste waters: Characterisation and feasibility study, Tellez, G.T., Nirmalakhandan, N., lntemational Produced Water Symposium Feb 4-7, 1992, San Diego Design of aerobic treatment units, Ramalho, R.S., Hydrocarbon processing, Part 1 and 2, Oct and Nov 1979 Removing VOCs from contaminated water: Part 1, Heilshorn, E.D., Chemical Engineering, March 1991 Oily effluent treatment by the BP Effluent treatment process, Oldham, G.F.. Sept 1979, EP 53584 Reduce oil and grease content in waste water, Capps, R.W.. Matelli, G.N., Bradford, M.L., Hydrocarbon Processing, June 1993 Evaluation of soluble oil and grease removal mechanisms in refinery wastewater treatment systems, P.T. Sun, R. van Compemolle, G.R. Mueller, J.J. Gentempo, Technical progress report WRC 122-86, MF 87-0254, Feb 87 The use of innovative biological reactors in the treatment of ground water contaminated with intermediate levels of aromatics, P.T. Sun, C.L. Price, G.W. Edmunds, Technical progress report WAC 4-87, MF 87-0863, July 87 Removing VOCs from contaminated water: Part 1, Heilshom, E.D.. Chemical Engineering, March 1991 Remove organics by activated carbon adsorption, Stenzel, M.H., Chemical Enqineering Practice, April 93 A fresh look at liquid-liquidextraction, Part 1: Extraction systems, Cusack, R.W., Fremeaux, P. Glatz, D., Chemical Engineering, Feb 1991 A fresh look at liquid-liquid extraction, Part 2: Inside the Extractor, Cusack, R.W., Fremeaux, P. Glatz, D., Chemical Engineering, Feb 1991 A fresh look at liquid-liquidextraction, Part 3: Cusack, R.W., Fremeaux, P. Glatz, D., Chemical Engineering, Apr 1991 Removal of hydrocarbons from effluent water, Equilibrium and kinetic measurements, Visser, H.P., Heexen. R., EW4, KSLA, 19 Oct 1990 Removal of dissolved hydrocarbons from effluent water using extraction, Jan -July 1992, Visser. H.P., Heezen, R., KSLA AMGR.90.285 Cooling water clean up by ozone, Echols, J.T., Mayne, S.T., Chemical engineering, May 1990 Waste water treatment by ozone oxidation, Berre Refinery, 1975 Looking to treat wastewater? Try ozone. Lin, S.H., Yeh, K.L., Chemical Engineering, May 1993 Investigations into the use of modified zeolites for removing benzene, toluene and xylene from saline produced waters, Janks, J.S., Cadena, F., International Produced Water Symposium Feb 4-7, 1992, San Diego OiVwater separation by membrane systems, Buss, G.Y., Vasmel, H, Schets, T.F.M, May 90, KSLA, prepared for the 1990 SlPM Production Technology Conference Treatment of produced water, Phase A, OLF report, May 1992 Peco (Perry Equipment Corporation) Filtration/Separation division, Equipment Manual Serck Baker, Fluid processing technology, Equipment Manual

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Additional stripping experiments using trays instead of packing in the column. Discusses the acclimatisation of micro-organisms for the biological treatment of saline production waters Discusses a range of aerobic treatment configurations and desiqn requirements Discusses general requirements for activated carbon adsorption and biological treatment systems Published BP paper discussing the selection of a effluent treatment system comprising media filters as a pre treatment followed by percolating filters for biological treatment. Discusses oily water treatment from the perspective of improving the performance of downstream biological treatment systems Discusses the breakdown of waste water from the Matinez manufacturing complex, particulady the presence of napthetic acids. Found that low molecular weight acids were biodegradable and higher MW acids could be absorbed onto activated carbon. Laboratory trials to investigate a Sludge Blanket Biological Reactor (SSBR), Aggregated Biological Solids Reactor (ABSR) and a Fluidised Bed Biofilm Reactor (FBBR) fro removal 10 mgA BTEX compounds. ABSR and FBBR recommended for pilot trials. Conceptual design proposed for a Aerated Biological Carbon Bed (ABCB). Discusses general requirements for activated carbon adsorption and biological treatment systems Discusses general requirements for activated carbon adsorption systems Discusses mass transfer theory behind liquid-liquid extraction systems Discusses the types of equipment behind liquid-liquid extraction systems Discusses pilot trials and scale up. Investigates liquid-liquid extraction of aromatics from water Discusses the results of experiments investigation a two stage extraction process. Discusses variables affecting the performance of the system. Although more orientated for controlling microbial growth, has some useful information on ozone systems. Discusses use of ozone alone for the removal of organics from water. Good results on phenols, BOD and COD reduction poor. Discusses the uses for ozone, including oxidation of organics and inorganics, as an alternative to chlorine. Discusses the methods for ozone generation and methods for effective dosing and use. Discusses background and use of modified zeolites on test waters and produced waters. Technology at a very early stage of development Summarises the results of the OWTC Phase 1 membrane trials and the pervaporation concept being tested by KSLA Extract of report discussing the various methods of dealing with heaw metals. Estimates equipment sizes for offshore . . installation. Includes equipment for liquid filtration, gas filtration/ separation, gas scrubbers, liquid phase separation, filter elements. Includes information on coarse filters, media filters, deaerators, reverse osmosis, ion exchange, static and rotary hydrocyclones, plate separators, dissolved gas flotation, chemical injection Includes information on oil/water skimmers, SP Packs, plate packs, hydrocyclones, flotation, caisson designs. Tested performance of Vortoil static cyclone, Dynaclean rotary cyclone and Wemco flotation cell. Tested performance of Vortoil static cyclone, Dynaclean rotary cyclone and Alfa Laval centrifuge. Significant problems with commissioning instruments. Trials not rigorously applied. Superseded by Phase II trials. Tested four membranes. See section 8.17 for more information

Ref.3.02.2.h Ref.3.03.1 .a

Ref.3.03.1 .b Ref.3.03.l.c Ref.3.03.1 .d Ref.3.03.1 .e Ref.3.03.1 .f

Ref.3.03.1 .g

Ref.3.M.l.a

I

I

I

I Ref.3.05.1 .a
Ref.3.05.1 .b Ref.3.05.1 .c Ref.3.05.2.a Ref.3.05.2.b Ref.3.99.1 .a Ref.3.99.l.b Ref.3.99.1 .c

Ref.3.M.1 .b

Ref.3.99.2

Ref.3.99.4 Ref.4.01 . I .a Ref.9.01 Ref.9.02

MPE, Modular production equipment, Equipment Manual Final report on the hydrocyclone/lGF trials conducted as the Orkney Water Test Centre, Nov 1988-Oct 1989. Tulloch, S.J., Jan 1990, EP-No.90-2641 Dynaclean and Vortoil hydrocyclones and Alfa Laval 3 phase disc stack centrifuge trials with condensate water mixes at Orkney Water Test Centre, Jan March 1987, Nezhati, K., May 1990, EP. N O 90-3599 Final report on the oil-in-water monitor testing conducted at Orkney Water Test Centre, February 1989 to October 1989, Tullock, S.J., March 1990, EP-No.90-3673 Membrane filter trials with various oily waters at Orkney Water Test Centre, Phase I, Nezhati, K., April 1991, EP-No.91-1017

Ref.9.03 Ref. OWTC EP 90-2641 Ref.OWTC EP 90-3599 Ref.OWTC EP 90-3673 Ref.OWTC EP 91-1017

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Puge BiDliogruphy-I2

SlPM Deoilinx Mmrtirl. EP 93-1315, Rrv 1.1, Nov 1993, File ncrrnr = 99ZZBIB.DOC

Oil in water trials conducted at the Orkney Water Test Centre, Phase II, November 1990 to March 1991, Tullock, S.J., Oct 1991, EP-N0.91-2151 Membrane filter trials with various oily waters at Orkney Water Test Centre, Phase 11, Nezhati, K., Sept 1991, EP-No.91-2152 Testing of coalescing devices to enhance the performance of hydrocyclones at Orkney Water Test Centre, Webster, J.D., March 1992, EP-No.92-0942 Comparative testing of new generation deoiling hydrocyclones by Orkney Water Test Centre, Tulloch, S.J., Aug 1992, EP 92-1900 Sulphate removal membrane filter trials, EP-No. 92-1905 Particle size analyser trials conducted at the Orkney Water Test Centre November 1990 February 1991, Tullock, S.J., Oct 1992, EP-N0.92-1952 Comparative testing 01 new generation deoiling hydrocyclones, Part 11, May 1993, EP. No. 93-1492

Performance of monitors improved. Variables investigated more rigorously Tested three membranes plus the Wemco Silver band litter. See section 8.17 for more inlormation on membranes. Wemco performance considered good. Investigates a range of coalescers including Knitmesh Dusec, Spiralsep, SP Pack, Sulzer Mellapak structured packing, and coalescing hydrocyclones. An appendum investigated the combined performance of coalescers and hydrocyclones, results were not as good as anticipated. Compared performance 01 Vortoil F liner Krebs, Hydropak and Hvdroswirl Investigates use of membranes lor sulphate removal from sea water. Compares a range of particle size analysers. Galai emerges as a strong contender having good performance and image analysis capabilities and can operate at process conditions. Compares performance of Vortoil F, G and K liners. Finds performance similar at high flows, large droplets, however K liner is superior for small droplets and low pressure drop Identified 34 different oil-in-water monitors from 19 vendors. Includes summaries of the operating method and range lor each instrument

Ref.OWTC EP 91-2151 Ref.OWTC EP 91-2152 Ref.OWTC EP 92-0942

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Rel.OWTC EP 92-1900 Ref.OWTC EP 92-1905 Ref.OWTC EP 92-1952 Ref.OWTC EP 93-1492 Rel.OWTC EP not assiqned

Further developments in oil-in-water monitor technology Phase II. Monitor selection, Desk study report", Tullock, S.J., June 1993

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SlPM Deotltng M(mrrcr/, EP 93-1315. Rev I I . Nov 1993, Frk tririlre = 99ZZBlB DOC

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Bibliography

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SIPM Deniliiih. M~rrivirl, &I’ 93.1315, Rev 1.I , Nov 1993. F#e ncinrr = 99ZZBlB.DOC

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